EP0185248B1 - Polyaddition or polycondensation products, their aqueous dispersions as well as a photographic recording material containing a photographic compound in the form of such polymeric products - Google Patents

Polyaddition or polycondensation products, their aqueous dispersions as well as a photographic recording material containing a photographic compound in the form of such polymeric products Download PDF

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Publication number
EP0185248B1
EP0185248B1 EP85115380A EP85115380A EP0185248B1 EP 0185248 B1 EP0185248 B1 EP 0185248B1 EP 85115380 A EP85115380 A EP 85115380A EP 85115380 A EP85115380 A EP 85115380A EP 0185248 B1 EP0185248 B1 EP 0185248B1
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European Patent Office
Prior art keywords
formula
compound
residue
alkyl
polyurethane
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EP85115380A
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German (de)
French (fr)
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EP0185248A3 (en
EP0185248A2 (en
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Günter Dr. Helling
Helmut Dr. Reiff
Friedrich-Wilhelm Dr. Kunitz
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Agfa Gevaert AG
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Agfa Gevaert AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3857—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur having nitrogen in addition to sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
    • G03C7/3882—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor characterised by the use of a specific polymer or latex
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/156—Precursor compound
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/156—Precursor compound
    • Y10S430/158—Development inhibitor releaser, DIR

Definitions

  • the invention relates to novel polyaddition or polycondensation products and a photographic recording material with at least one light-sensitive silver halide emulsion layer which contains a photographically useful compound in the form of such polyaddition or polycondensation products.
  • photographic recording materials are extremely complicated products and generally contain a large number of inorganic and organic constituents.
  • Such compounds are to be referred to as photographically useful compounds in the present context.
  • Photographically useful compounds in this sense are, for example, photographic couplers which, as a result of a coupling reaction with developer oxidation products, are able to form colored or non-colored coupling products, optionally with the liberation of a molecular residue which is directly, e.g.
  • Photographically useful compounds in this sense are furthermore, for example, compounds (photographic redox compounds) which, as a result of electron transfer, are able to release a molecular residue which is capable of contributing directly or indirectly to the construction of the image.
  • photographic couplers are color couplers (e.g. yellow, magenta, cyan couplers), white couplers, mask couplers, DIR couplers;
  • photographic redox compounds are oxidizable or reducible compounds which are able to release a dye as a result of oxidation or reduction (color releasers).
  • the photographic useful compounds diffuse as little as possible in the layers of the photographic recording materials.
  • they are usually provided with ballast residues, e.g. with straight-chain or branched alkyl radicals with 8 to 20 carbon atoms.
  • ballast residues e.g. with straight-chain or branched alkyl radicals with 8 to 20 carbon atoms.
  • the photographically useful compounds in the form of polymer dispersions in which the functional remainder of such a photographically useful compound is linked one or more times to a polymer structure and is thus made diffusion-resistant.
  • Such a polymer thus has recurring structural units with the functional rest of the relevant photographically useful compound.
  • Compounds useful in photography which are incorporated into the layers of photographic recording materials in the form of such polymer dispersions, are generally sufficiently diffusion-resistant and have little effect on the mechanical properties of the layers, even at low binder contents.
  • color couplers it is particularly important that they do not crystallize out during storage, have good stability against light, heat and moisture and that the dyes produced therefrom are also stable, have the desired spectral properties and during development diffusion-resistant and as fine a grain as possible.
  • Color couplers which are incorporated in the form of such polymer dispersions with a molecular weight greater than 5000 in photographic recording materials, generally have good colloidal stability and meet some of the demands made on them quite well.
  • Such high molecular weight color couplers are described for example in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A -33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211.
  • the high molecular weight color couplers are generally obtained by polymerizing ethylenically unsaturated so-called monomers Color couplers manufactured.
  • polymerizable emulsifiers DE-A-24 07 569, EP-A-27 284.
  • This did not solve the problem satisfactorily because residual portions of the monomeric emulsifier used or its hydrolysis products formed during the polymerization remain in the serum of the latex produced.
  • the polymeric latex couplers produced by polymerization furthermore do not show sufficient stability of the image dyes formed during development against heat, moisture or the action of UV light.
  • Another disadvantage of the known high-molecular color couplers is that, in comparison with low-molecular color couplers incorporated using oil formers, they have a higher wet scratch resistance, but also a lower breaking strength of the photographic recording materials.
  • the invention is based on the object of specifying photographically useful compounds, in particular photographic couplers or color splitters, in the form of polymer dispersions which can be prepared without emulsifiers and which have less tendency to foam and which, when incorporated into photographic colloid layers, result in improved mechanical properties and do not cause coating defects.
  • photographically useful compounds in particular photographic couplers or color splitters, in the form of polymer dispersions which can be prepared without emulsifiers and which have less tendency to foam and which, when incorporated into photographic colloid layers, result in improved mechanical properties and do not cause coating defects.
  • the photographically useful compounds are color couplers, the image dyes produced during development should have increased stability against heat, moisture or UV light. exhibit.
  • Q is the remainder of a photographically useful compound as previously defined, namely a compound which, when incorporated into a photographic material having at least one photosensitive silver halide emulsion layer, undergoes a chemical reaction under the development conditions in accordance with a previous imagewise exposure to produce desired colored or non-colored reaction products in image distribution.
  • Q is therefore e.g. the rest of a coupler or a photographic redox compound which, according to the invention, has been made sufficiently high molecular weight and thus diffusion-resistant by being linked to a polymer structure.
  • the residues of couplers can be residues of conventional 4-equivalent couplers as well as residues of 2-equivalent couplers, in which a smaller amount of silver halide is required to produce the color.
  • 2-equivalent couplers are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site, which is split off during the coupling.
  • the 2-equivalent couplers include both those that are practically colorless and those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced.
  • the latter couplers can serve as mask couplers to compensate for the undesired secondary densities of the image dyes.
  • the known white couplers are also to be counted among the 2-equivalent couplers, but they do not produce any dye when reacted with color developer oxidation products and thus only indirectly contribute to the construction of the color image.
  • the 2-equivalent couplers are also the known DIR couplers, which are couplers which contain a detachable residue in the coupling point, which is released as a diffusing development inhibitor when reacted with color developer oxidation products.
  • Other photographically active compounds such as, for example, nucleating or fogging agents, which can act as development accelerators, or hardening agents or bleaching catalysts, can preferably be released from such 2-equivalent couplers in a diffusible form and thereby activated.
  • the couplers can form yellow, purple or blue-green dyes of the most varied color gradations during development, depending on their chemical structure. Since the structures in question are sufficiently familiar to the person skilled in the art, their detailed explanation is not required at this point.
  • Redox-active groups and color releasers with such redox-active groups are known in a wide variety of embodiments. A detailed description can be found in the review article by Christian C. Van de Sande in Angew. Chem. 95, pp. 165-184 (1983).
  • the residue of a photographic redox compound represented by Q can contain, in place of a dye residue, another cleavable residue which, if necessary after image-wise release, can indirectly contribute to image formation, e.g. a development inhibitor, development accelerator, or a compound capable of reacting with developer oxidation products using the latter.
  • Preferred examples of the polyaddition or polycondensation products according to the invention contain recurring structural units of the following formula II: in what mean
  • the residues of photographically useful compounds represented by Q 'in formula II are basically the same type of residues of photographically useful compounds as are also represented and defined by Q in the formula. The difference is essentially only that, according to formula II, the connection of the photographically useful compound to the polymer backbone with both connection sites takes place via the same part of the molecule, while according to formula I the connection is left open.
  • the compounds of the formula III are synthesized by methods which are known in principle.
  • the preparation of the monomeric dihydroxy compound M-12 (purple coupler) is listed below for explanation.
  • reaction solution is concentrated in a mixture of 2.5 I ice / water and 500 ml. Hydrochloric acid.
  • the aqueous phase is decanted from oil. The oil is stirred twice with water and decanted.
  • the crude, still moist oil is dissolved in 1000 ml of alcohol and initially neutralized with 5N NaOH. 400 ml of 5N NaOH (2 mol) are added to the solution at room temperature. After 30 minutes, it is treated with activated carbon, filtered and acidified with acetic acid. The solution is stirred into 5 l of water. After 2 hours, it becomes crystal. Aspirated product and washed with water and methanol.
  • the individual structural elements of the formulas I and II are linked to one another by recurring structural units of the following formula IV, where Z is a (p + 1) -binding organic link and p is 1.
  • the polyaddition or polycondensation products according to the invention are therefore polyurea or polyurethane compounds which, in addition, can have a polyether and / or polyester structure in Group Z and, if appropriate, further ureido and / or urethane groups and also hydrophilic radicals.
  • Suitable starting materials for the structural units of the formula IV are compounds which have at least 2 isocyanate groups.
  • Monomeric polyisocyanates and their mixtures, multi-functional so-called NCO prepolymers and their mixtures, and also mixtures of monomeric polyisocyanates and multi-functional NCO prepolymers (semi-prepolymers) are suitable as such.
  • compounds with 2 isocyanate groups are preferably used, linear high-molecular polyaddition compounds are obtained according to the invention in which the individual structural elements of the formula I or II are linked to one another by recurring structural units of the formula IVa wherein Z 'represents the divalent radical of a diisocyanate compound.
  • the monomeric polyisocyanates are primarily diisocyanates, as are also mentioned below as starting materials for the preparation of the NCO prepolymers.
  • the NCO prepolymers are, for example, those which have one or more hydrophilic group (s) which determine their solubility or dispersibility in water.
  • the exact chemical structure of the NCO prepolymers is not critical. This means in particular that, according to the invention, all NCO prepolymers are suitable which have previously been used in the production of aqueous polyurethane dispersions or solutions.
  • polyisocyanates known per se in polyurethane chemistry, or else modified polyisocyanates (for example) containing carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups and / or biuret groups.
  • Any organic compounds with at least two groups which are reactive toward isocyanate groups in particular a total of two amino compounds, thiol groups, carboxyl groups and / or hydroxyl group-containing organic compounds of the molecular weight range 62 to 10,000, preferably 100 to 6,000 and in particular 500 to 4,000.
  • the corresponding ones are preferred Dihydroxy compounds used.
  • tri-functional or higher-functional compounds in the sense of the isocyanate polyaddition reaction in small proportions to achieve a certain degree of branching is possible, as is the possible use of tri- or higher-functional polyisocyanates mentioned above for the same purpose.
  • Hydroxyl compounds to be preferably used are the hydroxypolyesters, hydroxypolyethers, hydroxypolythioethers, hydroxypolyacetates, hydroxypolycarbonates and / or hydroxypolyesteramides known per se in polyurethane chemistry.
  • the hydroxyl group-containing polyesters are e.g. Reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polyhydric, preferably dihydric, carboxylic acids. Instead of the free carboxylic acids, their anhydrides or esters with lower alcohols can also be used to prepare the polyesters.
  • the polyvalent carboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally, e.g. by halogen atoms, substituted and / or unsaturated. Examples include:
  • Polyhydric alcohols include, for example, ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol (1,4) and - (2,3), hexanediol (1,6), octanediol (1, 8), neopentyl glycol, 1,4-bis-hydroxymethylcyclohexane, 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, hexanetriol (1,2,6), butanetriol (1,2,4), trimethylol ether, pentaerythritol , Quinite, mannitol and sorbitol, methyl glycoside, also diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycol in question.
  • the polyesters can have a proportion of terminal carboxyl groups
  • the polyethers which are also suitable, preferably having two hydroxyl groups are those of the type known per se and are obtained, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, for example in the presence of BF 3 or by addition these epoxides, optionally in a mixture or in succession, on starting components with reactive hydrogen atoms such as alcohols and amines, for example water, ethylene glycol, propylene glycol (1,3) or - (1,2), 4,4'-dihydroxydiphenylpropane, aniline.
  • epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin
  • reactive hydrogen atoms such as alcohols and amines
  • polyethers modified by vinyl polymers e.g. by polymerization of styrene / acrylonitrile in the presence of polyethers (US-A-3 383 351, US-A-3 304 273, US-A-3 523 093, US-A-3 110695, DE-C-1 152 536 ) are also suitable.
  • the proportionally higher-functionality polyethers to be used, if appropriate, are formed in an analogous manner by alkoxylation of higher-functionality starter molecules known per se, e.g. Ammonia, ethanolamine, ethylenediamine or sucrose.
  • the condensation products of thiodiglycol with itself and / or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols should be mentioned in particular.
  • the products are polythio mixed ethers, polythioether esters, polythioether ester amides.
  • hydroxypolyacetals e.g. the compounds which can be prepared from glycols, such as diethylene glycol, triethylene glycol, 4,4'-diethoxy-diphenyldimethylmethane, hexanediol and formaldehyde.
  • Suitable polyacetals can also be prepared by polymerizing cyclic acetals.
  • Suitable polycarbonates containing hydroxyl groups are those of the type known per se, which e.g. by reacting diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6), diethylene glycol, triethylene glycol, tetraethylene glycol with diaryl carbonates, e.g. Diphenyl carbonate or phosgene can be produced.
  • diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6)
  • diethylene glycol triethylene glycol
  • tetraethylene glycol e.g. Diphenyl carbonate or phosgene
  • the hydroxyl group-containing polyester amides and polyamides include e.g. the predominantly linear condensates obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines and their mixtures. Polyhydroxyl compounds already containing urethane or urea groups can also be used.
  • Low molecular weight polyols can also be used, e.g. Ethanediol, 1,2-propanediol and 1,3, 1,4-butanediol and 1,3, pentanediols, hexanediols, trimethylolpropane, hexanetriols, glycerol and pentaerythritol.
  • the preferred hydrophilically modified structural components include, in particular, the sulfonate group-containing aliphatic diols according to DE-A-2446440, the cationic or also anionic internal emulsifiers according to DE-A-26 51 506 and also the monofunctional built-in polyethers described there.
  • the reactants are generally used in such proportions that a ratio of isocyanate groups to hydrogen atoms which are reactive towards NCO, preferably from hydroxyl groups, is preferably from 1.05 to 10 from 1.1 to 3.
  • the order in which the individual reactants are added is largely arbitrary. You can either mix the hydroxyl compounds and add the polyisocyanate, or you can gradually add the mixture of hydroxyl compounds or the individual hydroxyl compounds to the polyisocyanate component.
  • the NCO prepolymers are preferably produced in the melt at 30 to 190 ° C., preferably at 50 to 120 ° C.
  • the preparation of the prepolymers can of course also be carried out in the presence of organic solvents, although a major advantage can be seen in the fact that such solvents are not required.
  • Suitable solvents e.g. to lower the viscosity of particularly high-melting prepolymers in amounts of up to 30% by weight, based on solids, would be, for example Acetone, methyl ethyl ketone, ethyl acetate, dimethylformamide, cyclohexanone, dioxane, glycol dimethyl ether, glycol ether acetates.
  • the preferred NCO prepolymers include those which are either ionic groups of the type mentioned under b), ie in particular -COO °, -S0 3 ° or or have nonionic groups of the type mentioned under c) or both ionic and nonionic groups of the type mentioned.
  • NCO prepolymers in the process according to the invention, in the production of which none of the hydrophilic structural components mentioned under 3. were used, in which the content of the groups mentioned under b) or c) is therefore 0.
  • dihydroxy or diamino compounds of the formula III and, if appropriate, further organic compounds having at least two groups which are reactive toward isocyanate groups are reacted with organic polyisocyanates.
  • the reaction can be carried out by first producing a bi- or polyfunctional NCO prepolymer by reacting the polyisocyanate with a first reactive compound, which is then reacted further with a second and optionally further reactive compound.
  • the photographically useful compound of formula 111 can be used as the first, second or also as a further reactive compound.
  • reaction conditions are familiar to the person skilled in the art. These are conditions under which polyurethanes or polyureas are usually produced. Those processes are preferably used in which the polyaddition or polycondensation product is obtained directly in the form of a dispersion or a latex.
  • the reaction mixture is then mixed with water to produce the aqueous solution or dispersion.
  • water Expediently, only enough water is used for this that the solution or dispersion has as high a solids content as possible.
  • Solutions or dispersions with a solids content of 30 to 60% by weight can preferably be prepared very well. Further dilution with water is easily possible.
  • the water is preferably added in one pour or gradually as desired.
  • the reaction mixture can also be mixed with water in such a way that the mixture is introduced into the aqueous phase. For example, water from 0 to 90 ° C, preferably from 15 to 60 ° C, is used.
  • the resulting dispersions are very fine, the particles preferably have a size of 20 to 200 nm, can of course also be larger.
  • the polyaddition or polycondensation products according to the invention can also be prepared with a plurality of such photographically useful compounds according to formula 111, it being possible for these different starting materials according to formula 111 to differ in the meaning of Q.
  • Q photographic functions
  • coupler units which supply different dyes in the case of color coupling in the polymer in order in this way to produce a mixed color in the case of color coupling.
  • other structural units of another function e.g. Install white coupler or DIR coupler units in a polymer.
  • the polyaddition or polycondensation products of the present invention can be incorporated into the casting solution of the silver halide emulsion layers or other colloid layers in a known manner, preferably by optionally in the form of aqueous dispersions, as can be obtained in the preparation, in The presence of a wetting or dispersing agent can be added to a hydrophilic colloid solution.
  • the hydrophilic casting solution can of course contain other conventional additives in addition to the binder.
  • the aqueous dispersion need not be directly dispersed in the casting solution for the silver halide emulsion layer or other water permeable layer; Rather, it can also be advantageously first dispersed in an aqueous, non-photosensitive solution of a hydrophilic colloid, whereupon the mixture obtained, after removal of the organic solvents used, may be mixed with the casting solution for the photosensitive silver halide emulsion layer or another water-permeable layer before application.
  • Suitable light-sensitive silver halide emulsions are emulsions of silver halide, silver bromide or mixtures thereof, possibly with a low siliodide content of up to 10 mol% in one of the commonly used hydrophilic binders.
  • Gelatin is preferably used as a binder for the photographic layers. However, this can be replaced in whole or in part by other natural or synthetic binders.
  • the emulsions can be chemically or spectrally sensitized in the usual way and the emulsion layers as well as other non-light-sensitive layers can be hardened in the usual way with known hardening agents.
  • the layers which contain the polyaddition or polycondensation products according to the invention, as well as other layers of the photographic recording material, can contain further additives in the usual way, e.g. Light stabilizers, UV absorbers, formalin scavengers, reducing agents, couplers and the like, it being possible for the additives mentioned to be present in polymeric form or in low molecular weight form.
  • the photographic recording material according to the invention generally contains at least three silver halide emulsion layers and associated color couplers, in which case at least one silver halide emulsion layer is assigned the corresponding color coupler in the form of one of the polyaddition or polycondensation products according to the invention.
  • the corresponding compound can be contained in the silver halide emulsion layer itself or in a non-light-sensitive binder layer adjacent to it. In this case, development is carried out with a paint roller.
  • Suitable color developer compounds are aromatic at least one primary amino group-containing compounds of the p-phenylenediamine type, for example, N, N-dialkyl-p-phenylenediamines, such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methylsulfonamidoethyl) -3-methyl-p-phenylenediamine , 1- (N-ethyl-N-hydroxyethyl-3-methyl-p-phenylenediamine) and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
  • Other silver halide developer compounds can also be used if the color imaging is not based on chromogenic development.
  • a mixture of 68 g of hexanediol-neopentyl glycol polyadipate (MW 1700), 131 g of compound M-1 and 50 ml of dry toluene are heated to approximately 100 ° C.
  • a mixture of 37 g of isophorone diisocyanate and 28 g of 1,6-hexamethylene diisocyanate is rapidly added dropwise at this temperature.
  • the clear solution is kept at 105-110 ° C for 3 h. After dilution with 720 ml acetone, the NCO titration gives a content of 3.3% NCO (calc. 3.7% NCO).
  • 397 g of this solution are mixed at 50 ° C. with a mixture of 18.4 g (50 mmol) of an aqueous solution of the sodium salt of ⁇ '-aminoethyl- ⁇ -aminoethanesulfonic acid and 25 ml of water. After approx. 10 min, the mixture is dispersed with 310 ml of deionized water and the solvent is removed in vacuo.
  • a mixture of 47.5 g of isophorone diisocyanate and 37.6 g is quickly added dropwise at 105 ° C. to a mixture of 85 g (0.05 mol) of hexanediol-neopentyl glycol polyadipate, 125 g of the compound M-12 and 500 ml of dry toluene 1,6-hexamethylene diisocyanate. After heating to 105-110 ° C for 2 hours, the toluene is distilled off. It is dissolved in 689 g of acetone. The NCO content is determined to be 2.7%.
  • a mixture of 50 ml of water and 40.1 g of a 51.6% strength aqueous solution of the sodium salt of ⁇ '-aminoethyl- ⁇ -aminoethanesulfonic acid is added to the acetone solution. After 10 min at 50 ° C., the mixture is dispersed with 675 ml of demineralized water and the solvent is removed in vacuo.
  • a dispersion is obtained with the following data:
  • a mixture of 35.1 g of hexamethylene diisocyanate and 46.4 g of isophorone diisocanate is rapidly added dropwise at 100 ° C. to a mixture of 126 g (0.074 mol) of hexanediol neopentyl glycol polyadipate, 93 g of the compound M-12 and 400 ml of dry dioxane. After 2 hours of heating at 100-108 0 C the NCO value is 2.9% (calculated: 3.0%). The dioxane is distilled off in vacuo and replaced by 740 ml of acetone.
  • a mixture of 21 g of a 51.6% strength aqueous solution of the sodium salt of ⁇ '-aminoethyl- ⁇ -aminoethanesulfonic acid and 50 g of water is then added at about 45 ° C. After 10 min, the mixture is dispersed with 830 ml of deionized water. The acetone is removed in vacuo and a finely divided, storage-stable dispersion is obtained with the following data:
  • aqueous dispersions of the polyaddition or polycondensation products according to the invention are incorporated into the layers of photographic recording materials by customary methods known to those skilled in the art.
  • a latex prepared as described above is added to a casting solution for a light-sensitive or non-light-sensitive layer and mixed intimately with it, whereupon the mixture is poured into the layer.
  • the casting solution generally contains a hydrophilic colloid as a binder, preferably gelatin.
  • the polyaddition or polycondensation product according to the invention can also be cast to form low-binder or largely binder-free layers.
  • the polyurethane magenta coupler latex D and E (example 4 and 5) and the comparative coupler A were mixed into different samples of a silver halide emulsion which was sensitized to blue or green according to the color coupler introduced.
  • the silver halide gelatin emulsion used consisted of 75 g of silver bromide iodide (iodide content 3 mol%) and 72 g of gelatin based on 1 kg of emulsion.
  • the emulsions prepared in this way were applied to cellulose triacetate layer supports provided with an adhesive layer and dried.
  • the polyurethane yellow coupler latex F and the comparative coupler B in the form of a dibutyl phthalate emulsion in aqueous gelatin were cast with a dibutyl phthalate / comparative coupler B ratio of 1: 1 as described in Example 1, exposed and processed. There were no significant differences in the sensitometric data.
  • the samples were also exposed to and without UV protective film (UV protective film with a 2-hydroxyphenylbenztriazole derivative as the absorbing substance) to the light of a xenon lamp standardized for daylight and exposed to 2.4.10 6 lux-h.
  • the percentage decrease in color density AD / Do given in Table 2 was measured.
  • Table 2 shows that the polyurethane yellow coupler latex according to the invention has an increased stability against harmful radiation compared to the comparative coupler.
  • the example shows the influence of the polyurethane yellow coupler latex F according to the invention on the breaking behavior of photographic recording materials.
  • a photographic emulsion layer consisting of a silver bromide emulsion, a dispersion prepared according to the invention or the comparative emulsifier from Example 2, gelatin and a hardening agent was prepared and dried on a prepared cellulose triacetate film support. After drying, the layer of the comparison material contained 30% by volume AgBr, 15% by volume Comparative Coupler B, 15% by volume dibutyl phthalate and 40% by volume gelatin.
  • an amount of polyurethane yellow coupler latex F which was equivalent in terms of the coupler units was used. 36 mm wide strips of these recording materials were 3 d in a climate of 20% RH. adjusted at 17 ° C.
  • the measurement was made using the loop method.
  • the test specimens are put together in a loop and rotated by 3 rollers, which are arranged in the shape of a triangle.
  • the number of revolutions which causes the film material to break is then determined and compared with a material which is produced as described above and contains 30% by volume AgBr and 70% by volume gelatin in layer components.
  • the measurements gave the following result:
  • the experiment shows that the use of the polyurethane latex couplers according to the invention improves the fracture behavior of photographic recording materials compared to those with emulsified color couplers.

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Description

Die Erfindung betrifft neuartige Polyadditions- bzw. Polykondensationsprodukte sowie ein fotografisches Aufzeichnungsmaterial mit mindestens einer lichtempfindlichen Silberhalogenidemulsionsschicht, das eine fotografisch nützliche Verbindung in Form solcher Polyadditions- bzw. Polykondensationsprodukte enthält.The invention relates to novel polyaddition or polycondensation products and a photographic recording material with at least one light-sensitive silver halide emulsion layer which contains a photographically useful compound in the form of such polyaddition or polycondensation products.

Fotografische Aufzeichnungsmaterialien sind bekanntlich äußerst kompliziert aufgebaute Produkte und enthalten in der Regel eine Vielzahl von anorganischen und organischen Bestandteilen. Hierunter verdienen besondere Erwähnung solche Verbindungen, die in dem Aufzeichnungsmaterial zunächst in gleichförmiger Verteilung enthalten sind, aber unter den Entwicklungsbedingungen nach Maßgabe einer vorausgegangenen bildmäßigen Belichtung bildmäßig einer chemischen Reaktion unterliegen unter Erzeugung gewünschter farbiger oder nicht farbiger Reaktionsprodukte in bildmäßiger Verteilung. Derartige Verbindungen sollen im vorliegenden Zusammenhang als fotografisch nützliche Verbindungen bezeichnet werden. Fotografisch nützliche Verbindungen in diesem Sinn sind beispielsweise fotografische Kuppler, die als Folge einer Kupplungsreaktion mit Entwickleroxidationsprodukten farbige oder nicht farbige Kupplungsprodukte zu bilden vermögen, gegebenenfalls unter Freisetzung eines Molekülrestes, der direkt, z.B. als Farbstoff, oder indirekt, z.B. als Entwicklungsinhibitor oder Entwicklungsakzelerator zum Aufbau des Bildes beizutragen imstande ist. Fotografisch nützliche Verbindungen in diesem Sinn sind weiterhin beispielsweise Verbindungen (fotografische Redoxverbindungen), die als Folge einer Elektronenübertragung einen Molekülrest freizusetzen vermögen, der direkt oder indirekt zum Aufbau des Bildes beizutragen imstande ist. Beispiele für fotografische Kuppler sind Farbkuppler (z.B. Gelb-, Magenta-, Cyankuppler), Weißkuppler, Maskenkuppler, DIR-Kuppler; Beispiele für fotografische Redoxverbindungen sind oxidierbare oder reduzierbare Verbindungen, die als Folge einer Oxidation bzw. Reduktion einen Farbstoff freizusetzen vermögen (Farbabspalter).As is known, photographic recording materials are extremely complicated products and generally contain a large number of inorganic and organic constituents. Among these, special mention should be given to those compounds which are initially contained in the recording material in a uniform distribution, but are subject to a chemical reaction under the development conditions in accordance with a previous imagewise exposure to produce a desired colored or non-colored reaction product in an imagewise distribution. Such compounds are to be referred to as photographically useful compounds in the present context. Photographically useful compounds in this sense are, for example, photographic couplers which, as a result of a coupling reaction with developer oxidation products, are able to form colored or non-colored coupling products, optionally with the liberation of a molecular residue which is directly, e.g. as a dye, or indirectly, e.g. is able to contribute to the development of the image as a development inhibitor or development accelerator. Photographically useful compounds in this sense are furthermore, for example, compounds (photographic redox compounds) which, as a result of electron transfer, are able to release a molecular residue which is capable of contributing directly or indirectly to the construction of the image. Examples of photographic couplers are color couplers (e.g. yellow, magenta, cyan couplers), white couplers, mask couplers, DIR couplers; Examples of photographic redox compounds are oxidizable or reducible compounds which are able to release a dye as a result of oxidation or reduction (color releasers).

Es ist in der Regel erwünscht, daß die fotografische nützlichen Verbindungen in den Schichten der fotografischen Aufzeichnungsmaterialien möglichst wenig diffundieren. Zu diesem Zweck sind sie normalerweise mit Ballastresten versehen, z.B. mit gradkettigen oder verzweigten Alkylresten mit 8 bis 20 C-Atomen. Es ist auch bekannt die fotografisch nützlichen Verbindungen in Form von Polymerisatdispersionen zu verwenden, in denen der funktionelle Rest einer solchen fotografisch nützlichen Verbindung ein- oder mehrfach mit einem Polymergerüst verknüpft und auf diese Weise diffusionsfest gemacht ist. Ein solches Polymer weist somit wiederkehrende Struktureinheiten mit dem funktionellen Rest der betreffenden fotografisch nützlichen Verbindung auf.It is generally desirable that the photographic useful compounds diffuse as little as possible in the layers of the photographic recording materials. For this purpose they are usually provided with ballast residues, e.g. with straight-chain or branched alkyl radicals with 8 to 20 carbon atoms. It is also known to use the photographically useful compounds in the form of polymer dispersions in which the functional remainder of such a photographically useful compound is linked one or more times to a polymer structure and is thus made diffusion-resistant. Such a polymer thus has recurring structural units with the functional rest of the relevant photographically useful compound.

Fotografisch nützliche Verbindungen, die in Form solcher Polymerisatdispersionen in die Schichten von fotografischen Aufzeichnungsmaterialien eingearbeitet sind, sind im allgemeinen ausreichend diffusionsrest und beeinträchtigen die mechanischen Eigenschaften der Schichten auch bei geringen Bindemittelgehalten nur wenig. Wenn es sich um Farbkuppler handelt, dann ist es besonders wichtig, daß sie bei der Lagerung nicht auskristallisieren, eine gute Stabilität gegen Licht, Wärme und Feuchtigkeit aufweisen und daß auch die daraus erzeugten Farbstoffe stabil sind, die erwünschten spektralen Eigenschaften aufweisen und bei der Entwicklung diffusionsfest und als möglichst feines Korn abgeschieden werden. Farbkuppler, die in Form solcher Polymerisatdispersionen mit einem Molekulargewicht größer als 5000 in fotografische Aufzeichnungsmaterialien eingearbeitet sind, weisen allgemein gute Kolloidstabilität auf und erfüllen einige der genannten an sie gerichteten Forderungen recht gut. Solche hochmolekularen Farbkuppler sind beispielsweise beschrieben in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211. Die hochmolekularen Farbkuppler werden in der Regel durch Polymerisation von ethylenisch ungesättigten sogenannten monomeren Farbkupplern hergestellt. Sie erweisen sich jedoch mindestens insoweit als nachteilig als zu ihrer Herstellung vergleichsweise hohe Emulgatormengen (z.B. 5-8%, bezogen auf den polymeren Kuppler) erforderlich sind, was bei der Verarbeitung eine unerwünschte Schaumbildung zur Folge hat mit der weiteren Folge, daß die mit solchen Polymerisatdispersionen vergossenen Schichten häufig Punktfehler, Streifen oder ähnliche Beschichtungsfehler aufweisen.Compounds useful in photography, which are incorporated into the layers of photographic recording materials in the form of such polymer dispersions, are generally sufficiently diffusion-resistant and have little effect on the mechanical properties of the layers, even at low binder contents. When it comes to color couplers, it is particularly important that they do not crystallize out during storage, have good stability against light, heat and moisture and that the dyes produced therefrom are also stable, have the desired spectral properties and during development diffusion-resistant and as fine a grain as possible. Color couplers, which are incorporated in the form of such polymer dispersions with a molecular weight greater than 5000 in photographic recording materials, generally have good colloidal stability and meet some of the demands made on them quite well. Such high molecular weight color couplers are described for example in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A -33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211. The high molecular weight color couplers are generally obtained by polymerizing ethylenically unsaturated so-called monomers Color couplers manufactured. However, they prove to be disadvantageous at least insofar as comparatively high amounts of emulsifier (for example 5-8%, based on the polymeric coupler) are required for their production, which results in undesirable foam formation during processing, with the further consequence that those with such Polymer dispersions cast layers often have point defects, streaks or similar coating defects.

Um die Neigung zum Schäumen zu reduzieren wurde empfohlen, einpolymerisierbare Emulgatoren zu verwenden (DE-A-24 07 569, EP-A-27 284). Jedoch konnte hierdurch das Problem nicht befriedigend gelöst werden, weil Restanteile des verwendeten monomeren Emulgators oder dessen bei der Polymerisation gebildete Hydrolyseprodukte im Serum des erzeugten Latex verbleiben. Die durch Polymerisation hergestellten polymeren Latexkuppler zeigen weiterhin keine ausreichende Stabilität der bei der Entwicklung gebildeten Bildfarbstoffe gegenüber Wärme, Feuchtigkeit oder der Einwirkung von UV-Licht. Ein weiterer Nachteil der bekannten hochmolekularen Farbkuppler besteht darin, daß sie im Vergleich mit niedermolekularen, unter Verwendung von Ölbildnern eingearbeiteten Farbkupplern zwar eine höher Naßkratzfestigkeit, aber auch eine geringere Bruchfestigkeit der fotografischen Aufzeichnungsmaterialien bewirken.In order to reduce the tendency to foam, it was recommended to use polymerizable emulsifiers (DE-A-24 07 569, EP-A-27 284). However, this did not solve the problem satisfactorily because residual portions of the monomeric emulsifier used or its hydrolysis products formed during the polymerization remain in the serum of the latex produced. The polymeric latex couplers produced by polymerization furthermore do not show sufficient stability of the image dyes formed during development against heat, moisture or the action of UV light. Another disadvantage of the known high-molecular color couplers is that, in comparison with low-molecular color couplers incorporated using oil formers, they have a higher wet scratch resistance, but also a lower breaking strength of the photographic recording materials.

Der Erfindung liegt die Aufgabe zugrunde, fotografisch nützliche Verbindungen, insbesondere fotografische Kuppler oder Farbspalter, in Form von emulgatorfrei herstellbaren Polymerdispersionen anzugeben, die weniger zum Schäumen neigen und bei Einarbeitung in fotografische Kolloidschichten verbesserte mechanische Eigenschaften ergeben und keine Beschichtungsfehler hervorrufen. Weiterhin sollen, wenn es sich bei den fotografisch nützlichen Verbindungen um Farbkuppler handelt, die bei Entwicklung erzeugten Bildfarbstoffe erhöhte Stabilität gegenüber Wärme, Feuchtigkeit oder UV-Licht . aufweisen.The invention is based on the object of specifying photographically useful compounds, in particular photographic couplers or color splitters, in the form of polymer dispersions which can be prepared without emulsifiers and which have less tendency to foam and which, when incorporated into photographic colloid layers, result in improved mechanical properties and do not cause coating defects. Farther If the photographically useful compounds are color couplers, the image dyes produced during development should have increased stability against heat, moisture or UV light. exhibit.

Die Aufgabe wurde gelöst mit neuartigen hochmolekularen Polyadditions- bzw. Polykondensationsprodukten, die wiederkehrende Struktureinheiten der folgenden Formel enthalten:

Figure imgb0001
worin bedeuten

  • Q den n-bindigen Rest einer fotografisch nützlichen Verbindung
  • Y -0- oder -NR'-
  • R' H, Alkyl mit 1 bis 6 C-Atomen, Cycloalkyl oder Phenyl
  • n eine Zahl von 2 bis 4, vorzugsweise 2
The problem was solved with novel high-molecular polyaddition or polycondensation products which contain recurring structural units of the following formula:
Figure imgb0001
 in what mean
  • Q the n-bonded residue of a photographically useful compound
  • Y -0- or -NR'-
  • R 'H, alkyl having 1 to 6 carbon atoms, cycloalkyl or phenyl
  • n is a number from 2 to 4, preferably 2

Q ist der Rest einer fotografisch nützlichen Verbindung wie zuvor definiert, nämlich einer Verbindung, die, wenn sie in ein fotografisches Aufzeichnungsmaterial mit mindestens einer lichtempfindlichen Silberhalogenidemulsionsschicht eingearbeitet ist, unter den Entwicklungsbedingungen nach Maßgabe einer vorausgegangenen bildmäßigen Belichtung einer chemischen Reaktion unterliegt unter Erzeugung gewünschter farbiger oder nicht farbiger Reaktionsprodukte in bildmäßiger Verteilung. Q ist demnach z.B. der Rest eines Kupplers oder einer fotografischen Redoxverbindung, die erfindungsgemäß durch Verknüpfung mit einem Polymergerüst ausreichend hochmolekular und dadurch diffusionsfest gemacht worden ist.Q is the remainder of a photographically useful compound as previously defined, namely a compound which, when incorporated into a photographic material having at least one photosensitive silver halide emulsion layer, undergoes a chemical reaction under the development conditions in accordance with a previous imagewise exposure to produce desired colored or non-colored reaction products in image distribution. Q is therefore e.g. the rest of a coupler or a photographic redox compound which, according to the invention, has been made sufficiently high molecular weight and thus diffusion-resistant by being linked to a polymer structure.

Bei den Resten von Kupplern kann es sich sowohl um Reste üblicher 4-Äquivalentkuppler handeln als auch um Reste von 2-Äquivalentkupplern, bei denen zur Farberzeugung eine geringere Menge Silberhalogenid erforderlich ist. 2-Äquivalentkuppler leiten sich bekanntlich von den 4-Äquivalentkupplern dadurch ab, daß sie in der Kupplungsstelle einen Substituenten enthalten, der bei der Kupplung abgespalten wird. Zu den 2-Äquivalentkupplern sind sowohl solche zu rechnen, die praktisch farblos sind, als auch solche, die eine intensive Eigenfarbe aufweisen, die bei der Farbkupplung verschwindet bzw. durch die Farbe des erzeugten Bildfarbstoffes ersetzt wird. Letztere Kuppler können als Maskenkuppler zur Kompensierung der unerwäunschten Nebendichten der Bildfarbstoffe dienen. Zu den 2-Äquivalentkupplern sich auch die bekannten Weißkuppler zu rechnen, die jedoch bei Reaktion mit Farbentwickleroxidationsprodukten keinen Farbstoff ergeben und somit nur indirekt zum Aufbau des Farbbildes beitragen. Zu den 2-Äquivalentkupplern sind ferner die bekannten DIR-Kuppler zu rechnen, bei denen es sich um Kuppler handelt, die in der Kupplungsstelle einen abspaltbaren Rest enthalten, der bei Reaktion mit Farbentwickleroxidationsprodukten als diffundierender Entwicklungsinhibitor in Freiheit gesetzt wird. Auch andere fotografisch wirksame Verbindungen wie beispielsweise keimbildende oder verschleiernde Agentien, die als Entwicklungsakzelerator wirken können, oder Härtungsmittel oder Bleichkatalysatoren können aus solchen 2-Äquivalentkupplern bevorzugt in diffusionsfähiger Form freigesetzt und dadurch aktiviert werden. Als Farbkuppler können die Kuppler bei der Entwicklung gelbe, purpurne oder blaugrüne Farbstoffe der verschiedensten Farbabstufungen bilden, je nach ihrer chemischen Struktur. Da die hierfür in Frage kommenden Strukturen dem Fachmann ausreichend geläufig sind, bedarf es an dieser Stelle nicht ihrer ausführlichen Erläuterung.The residues of couplers can be residues of conventional 4-equivalent couplers as well as residues of 2-equivalent couplers, in which a smaller amount of silver halide is required to produce the color. As is well known, 2-equivalent couplers are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site, which is split off during the coupling. The 2-equivalent couplers include both those that are practically colorless and those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced. The latter couplers can serve as mask couplers to compensate for the undesired secondary densities of the image dyes. The known white couplers are also to be counted among the 2-equivalent couplers, but they do not produce any dye when reacted with color developer oxidation products and thus only indirectly contribute to the construction of the color image. Among the 2-equivalent couplers are also the known DIR couplers, which are couplers which contain a detachable residue in the coupling point, which is released as a diffusing development inhibitor when reacted with color developer oxidation products. Other photographically active compounds, such as, for example, nucleating or fogging agents, which can act as development accelerators, or hardening agents or bleaching catalysts, can preferably be released from such 2-equivalent couplers in a diffusible form and thereby activated. As color couplers, the couplers can form yellow, purple or blue-green dyes of the most varied color gradations during development, depending on their chemical structure. Since the structures in question are sufficiently familiar to the person skilled in the art, their detailed explanation is not required at this point.

Bei den Resten von Farbabspaltern kann es sich um Reste einer Vielfalt von Verbindungstypen handeln, die sich sämtlich durch einen Chromophor und ein in seiner Bindungsfestigkeit redoxabhängiges Bindeglied auszeichnen, welches den Chromophor mit dem diffusionsfest machenden Polymergerüst verknüpft. Solche Verbindungen enthalten demnach eine Gruppe der Formel

Figure imgb0002
worin bedeuten

  • REDOX eine redoxaktive Gruppe, d.h. eine Gruppe, die unter den Bedingungen der alkalischen Entwicklung oxidierbar oder reduzierbar ist und je nachdem, ob sie im oxidierten oder im reduzierten Zustand vorliegt, in unterschiedlichem Ausmaß einer Eliminierungsreaktion, einer nukleophilen Verdrängungsreaktion, einer Hydrolyse oder einer sonstigen Spaltungsreaktion unterliegt mit der Folge, daß der Rest FARBSTOFF abgespalten wird, und
  • FARBSTOFF den Rest eines diffusionsfähigen Farbstoffes.
The residues of color releasers can be residues of a variety of connection types, all of which are characterized by a chromophore and a linkage which is redox-dependent in terms of its binding strength and which links the chromophore to the diffusion-resistant polymer structure. Such compounds accordingly contain a group of the formula
Figure imgb0002
 in what mean
  • REDOX is a redox-active group, i.e. a group that can be oxidized or reduced under the conditions of alkaline development and, depending on whether it is in the oxidized or in the reduced state, to different degrees of an elimination reaction, a nucleophilic displacement reaction, a hydrolysis or another cleavage reaction is subject to the result that the rest of DYE is split off, and
  • DYE the rest of a diffusible dye.

Redoxaktive Gruppen und Farbabspalter mit solchen redoxaktiven Gruppen sind in den verschiedensten Ausführungsformen bekannt. Eine detaillierte Darstellung findet man in dem Übersichtsartikel von Christian C. Van de Sande in Angew. Chem. 95, S. 165-184 (1983). Selbstverständlich kann der durch Q dargestellte Rest einer fotografischen Redoxverbindung anstelle eines Farbstoffrestes einen sonstigen abspaltbaren Rest enthalten, der gegebenenfalls nach bildmäßiger Freisetzung indirekt zum Bildaufbau beizutragen imstande ist, z.B. einen Entwicklungsinhibitor, Entwicklungsakzelerator oder eine Verbindung die mit Entwickleroxidationsprodukten unter Verbrauch der letzteren zu reagieren vermag.Redox-active groups and color releasers with such redox-active groups are known in a wide variety of embodiments. A detailed description can be found in the review article by Christian C. Van de Sande in Angew. Chem. 95, pp. 165-184 (1983). Of course, the residue of a photographic redox compound represented by Q can contain, in place of a dye residue, another cleavable residue which, if necessary after image-wise release, can indirectly contribute to image formation, e.g. a development inhibitor, development accelerator, or a compound capable of reacting with developer oxidation products using the latter.

Bevorzugte Beispiele der erfindungsgemäßen Polyadditions- bzw. Polykondensationsprodukte enthalten wiederkehrende Struktureinheiten der folgenden Formel II:

Figure imgb0003
worin bedeutenPreferred examples of the polyaddition or polycondensation products according to the invention contain recurring structural units of the following formula II:
Figure imgb0003
 in what mean

Q' entweder alleine oder zusammen mit X (unter Einbeziehung von ―L1―A3―L2―) den Rest einer fotografisch nützlichen Verbindung

Figure imgb0004
Figure imgb0005

  • A1, A2 Alkylen mit 1 bis 4 C-Atomen
  • A3 Alkylen mit 1 bis 8 C-Atomen, Arylen oder eine chemische Bindung
  • L1 -CONH-, -NHCO-, -CO-, ―SO2―, -0- oder eine chemische Bindung
  • L2 ―CONH―, -NH-, -0- oder eine chemische Bindung
  • R1 H, Alkyl mit 1 bis 6 C-Atomen, Cycloalkyl oder Phenyl
  • R2 H oder Alkyl mit 1 bis 4 C-Atomen.
Q 'either alone or together with X (including ―L 1 ―A 3 ―L 2 -) the rest of a photographically useful compound
Figure imgb0004
Figure imgb0005
  • A 1 , A 2 alkylene with 1 to 4 carbon atoms
  • A 3 alkylene with 1 to 8 carbon atoms, arylene or a chemical bond
  • L 1 -CONH-, -NHCO-, -CO-, ―SO 2 -, -0- or a chemical bond
  • L 2 ―CONH―, -NH-, -0- or a chemical bond
  • R 1 H, alkyl with 1 to 6 carbon atoms, cycloalkyl or phenyl
  • R 2 H or alkyl with 1 to 4 carbon atoms.

Bei den in Formel II durch Q' dargestellten Resten fotografisch nützlicher Verbindungen handelt es sich grundsätzlich um die gleiche Art von Resten fotografisch nützlicher Verbindungen, wie sie auch in Formel durch Q dargestellt und definiert werden. Der Unterschied liegt im wesentlichen nur darin, daß nach Formel II die Anknüpfung der fotografisch nützlichen Verbindung an das Polymergerüst mit beiden Verknüpfungsstellen über denselben Molekülteil erfolgt, während nach Formel I die Anknüpfung offengelassen ist.The residues of photographically useful compounds represented by Q 'in formula II are basically the same type of residues of photographically useful compounds as are also represented and defined by Q in the formula. The difference is essentially only that, according to formula II, the connection of the photographically useful compound to the polymer backbone with both connection sites takes place via the same part of the molecule, while according to formula I the connection is left open.

Als Ausgangsmaterial für die wiederkehrenden Struktureinheiten der Formel I eignen sich Verbindungen der allgemeinen Formel III

Figure imgb0006
worin Y, Q und n die bereits angegebene Bedeutung haben.Compounds of the general formula III are suitable as starting material for the recurring structural units of the formula I.
Figure imgb0006
 where Y, Q and n have the meaning already given.

Beispiele hierfür sind im folgenden aufgeführt.

Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028
Figure imgb0029
Figure imgb0030
Figure imgb0031
Figure imgb0032
Figure imgb0033
Figure imgb0034
Figure imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038
Figure imgb0039
Figure imgb0040
Figure imgb0041
Figure imgb0042
Figure imgb0043
Figure imgb0044
Figure imgb0045
Figure imgb0046
Figure imgb0047
Figure imgb0048
Figure imgb0049
Figure imgb0050
Figure imgb0051
Figure imgb0052
Figure imgb0053
Figure imgb0054
Figure imgb0055
Figure imgb0056
 Examples of these are listed below.
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028
Figure imgb0029
Figure imgb0030
Figure imgb0031
Figure imgb0032
Figure imgb0033
Figure imgb0034
Figure imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038
Figure imgb0039
Figure imgb0040
Figure imgb0041
Figure imgb0042
Figure imgb0043
Figure imgb0044
Figure imgb0045
Figure imgb0046
Figure imgb0047
Figure imgb0048
Figure imgb0049
Figure imgb0050
Figure imgb0051
Figure imgb0052
Figure imgb0053
Figure imgb0054
Figure imgb0055
Figure imgb0056

Die Synthese der Verbindungen der Formel III erfolgt nach grundsätzlich bekannten Methoden. Zur Erläuterung ist im folgenden die Herstellung der monomeren Dihydroxyverbindung M-12 (Purpurkuppler) aufgeführt.The compounds of the formula III are synthesized by methods which are known in principle. The preparation of the monomeric dihydroxy compound M-12 (purple coupler) is listed below for explanation.

Stufe 1: 2,2-BisacetoxymethylpropionsäureStep 1: 2,2-bisacetoxymethyl propionic acid

268 g (2 mol) 2,2-Bishydroxymethylpropionsäure werden in 800 ml Eisessig und 416 ml (4,4 mol) Essigsäureanhydrid 10 h am Rückfluß gekocht. Die Reaktionslösung wird im Vakuum vom Lösungsmittel befreit. Der ölige Rückstand wird mit 1500 ml Petrolether verrührt. Dabei kristallisiert die Estercarbonsäure aus. Sie wird abgesaugt und mit Petrolether gewaschen. Ausbeute 420 g (96% d.Th.); Fp. 85°C.268 g (2 mol) of 2,2-bishydroxymethylpropionic acid are refluxed in 800 ml of glacial acetic acid and 416 ml (4.4 mol) of acetic anhydride for 10 hours. The reaction solution is freed from the solvent in vacuo. The oily residue is stirred with 1500 ml of petroleum ether. The ester carboxylic acid crystallizes out. It is suctioned off and washed with petroleum ether. Yield 420 g (96% of theory); Mp 85 ° C.

Stufe 2: 2,2-BisacetoxymethylpropionsäurechloridStep 2: 2,2-bisacetoxymethyl propionic acid chloride

218 g (1 mol) 2,2-Bisacetoxymethylpropionsäure (Stufe 1) werden mit 182 ml (2,5 mol) Thionylchlorid übergossen und 8 h lang bei einer Badtemperatur von ca. 100°C am Rückfluß gekocht. Überschüssiges Thionylchlorid wird unter Wasserstrahlvakuum abdestilliert. Es resultiert ein schwach gelbes öliges Produkt. Ausbeute 236 g (100% d.Th.).218 ml (2.5 mol) of thionyl chloride are poured over 218 g (1 mol) of 2,2-bisacetoxymethylpropionic acid (stage 1) and the mixture is refluxed for 8 hours at a bath temperature of approx. 100 ° C. Excess thionyl chloride is distilled off under a water jet vacuum. The result is a slightly yellow oily product. Yield 236 g (100% of theory).

Stufe 3: Verbindung M-12Stage 3: compound M-12

111,4 g (0,4 mol) 1-(2,4,6-Trichlorphenyl)-3-aminopyrazolon(5) werden in 500 ml Acetonitril angeschlemmt. Es werden 77,2 ml (0,8 mol) Pyridin hinzugegeben. Bei Raumtemperatur werden 189 g (0,8 mol) 2,2-Bisacetoxymethylpropionsäurechlorid innerhalb von 20 min eingetropft. Das Aminopyrazolon geht dabei in Lösung.111.4 g (0.4 mol) of 1- (2,4,6-trichlorophenyl) -3-aminopyrazolone (5) are suspended in 500 ml of acetonitrile. 77.2 ml (0.8 mol) of pyridine are added. At room temperature, 189 g (0.8 mol) 2,2-bisacetoxymethylpropionoyl chloride added dropwise within 20 min. The aminopyrazolone goes into solution.

Die Reaktionslösung wird in eine Mischung von 2,5 I Eis/Wasser und 500 ml konz. Salzsäure ausgerührt. Die wäßrige Phase wird von Öl abdekantiert. Das Öl wird noch 2 mal mit Wasser verrührt und dekantiert.The reaction solution is concentrated in a mixture of 2.5 I ice / water and 500 ml. Hydrochloric acid. The aqueous phase is decanted from oil. The oil is stirred twice with water and decanted.

Das rohe, noch feuchte Öl wird in 1000 ml Alkohol gelöst und mit 5n NaOH zunächst neutral gestellt. Die Lösung wird mit 400 ml 5n NaOH (2 mol) bei Raumtemperatur versetzt. Nach 30 min wird mit Aktivkohle behandelt, filtriert und mit Essigsäure sauergestellt. Die Lösung wird in 5 I Wasser eingerührt. Nach 2 h wird das krist. Produkt abgesaugt und mit Wasser und Methanol gewaschen.The crude, still moist oil is dissolved in 1000 ml of alcohol and initially neutralized with 5N NaOH. 400 ml of 5N NaOH (2 mol) are added to the solution at room temperature. After 30 minutes, it is treated with activated carbon, filtered and acidified with acetic acid. The solution is stirred into 5 l of water. After 2 hours, it becomes crystal. Aspirated product and washed with water and methanol.

Es werden 86 g (54% d.Th.) eines schwach gelblichen Kristallisates vom Fp. 227-229°C erhalten.86 g (54% of theory) of a slightly yellowish crystallizate of mp 227-229 ° C. are obtained.

In den erfindungsgemäßen hochmolekularen Polyadditions- bzw. Polykondensationsprodukten sind die einzelnen Strukturelemente der Formeln I bzw. II untereinander durch wiederkehrende Struktureinheiten der folgenden Formel IV verknüpft,

Figure imgb0057
worin Z ein (p + 1)-bindiges organisches Bindeglied bedeutet und p 1 ist. Es handelt sich somit bei den erfindungsgemäßen Polyadditions- bzw. Polykondensationsprodukten um Polyharnstoff- oder Polyurethanverbindungen, die darüber hinaus in der Gruppe Z noch Polyether- und/oder Polyesterstruktur sowie gegebenenfalls weitere Ureido- und/oder Urethangruppen sowie ferner auch hydrophile Reste aufweisen können.In the high molecular weight polyaddition or polycondensation products according to the invention, the individual structural elements of the formulas I and II are linked to one another by recurring structural units of the following formula IV,
Figure imgb0057
 where Z is a (p + 1) -binding organic link and p is 1. The polyaddition or polycondensation products according to the invention are therefore polyurea or polyurethane compounds which, in addition, can have a polyether and / or polyester structure in Group Z and, if appropriate, further ureido and / or urethane groups and also hydrophilic radicals.

Geeignete Ausgangsmaterialien für die Struktureinheiten der Formel IV sind Verbindungen, die mindestens 2 Isocyanatgruppen aufweisen. Als solche kommen in Frage monomere Polyisocyanate und deren Gemische, mehrfunktionelle sogenannte NCO-Präpolymere und deren Gemische, sowie auch Gemische von monomeren Polyisocyanaten und mehrfunktionellen NCO-Präpolymeren (Semipräpolymere). Beim bevorzugten Einsatz von Verbindungen mit 2 Isocyanatgruppen werden erfindungsgemäß lineare hochmolekulare Polyadditionsverbindungen erhalten, in denen die einzelnen Strukturelemente der Formel I bzw. II untereinander durch wiederkehrende Struktureinheiten der Formel IVa verknüpft sind

Figure imgb0058
worin Z' den zweiwertigen Rest einer Diisocyanatverbindung bedeutet.Suitable starting materials for the structural units of the formula IV are compounds which have at least 2 isocyanate groups. Monomeric polyisocyanates and their mixtures, multi-functional so-called NCO prepolymers and their mixtures, and also mixtures of monomeric polyisocyanates and multi-functional NCO prepolymers (semi-prepolymers) are suitable as such. When compounds with 2 isocyanate groups are preferably used, linear high-molecular polyaddition compounds are obtained according to the invention in which the individual structural elements of the formula I or II are linked to one another by recurring structural units of the formula IVa
Figure imgb0058
 wherein Z 'represents the divalent radical of a diisocyanate compound.

Bei den monomeren Polyisocyanaten handelt es sich in erster Linie um Diisocyanate, wie sie nachstehend auch als Ausgangsmaterialien zur Herstellung der NCO-Präpolymere erwähnt werden. Bei den NCO-Präpolymeren handelt es sich beispielsweise um solche, die eine oder mehrere ihre Löslichkeit bzw. Dispergierbarkeit in Wasser bedingende hydrophile Gruppierung(en) aufweisen. Der genaue chemische Aufbau der NCO-Präpolymeren ist jedoch nicht kritisch. Dies bedeutet insbesondere, daß erfindungsgemäß alle NCO-Präpolymeren geeignet sind, die bislang bereits bei der Herstellung von wäßrigen Polyurethan-Dispersionen oder -lösungen zum Einsatz gelangten. Ihre Herstellung erfolgt nach bekannten Verfahren des Standes der Technik und ist beispielsweise in DE-A-1 495 745, DE-A-1 495 847, DE-A-24 46 440, DE-A-23 40 512, US―A―3479 310, GB-A-1 158 088 oder GB-A-1 076 688 beschrieben.The monomeric polyisocyanates are primarily diisocyanates, as are also mentioned below as starting materials for the preparation of the NCO prepolymers. The NCO prepolymers are, for example, those which have one or more hydrophilic group (s) which determine their solubility or dispersibility in water. However, the exact chemical structure of the NCO prepolymers is not critical. This means in particular that, according to the invention, all NCO prepolymers are suitable which have previously been used in the production of aqueous polyurethane dispersions or solutions. They are produced by known processes of the prior art and are described, for example, in DE-A-1 495 745, DE-A-1 495 847, DE-A-24 46 440, DE-A-23 40 512, US ― A― 3479 310, GB-A-1 158 088 or GB-A-1 076 688.

Die Herstellung der beim erfindungsgemäßen Verfahren bevorzugt einzusetzenden NCO-Präpolymeren mit chemisch eingebauten hydrophilen Gruppen geschieht in Analogie zu den Methoden, wie sie in den beispielhaft genannten Literaturstellen genannt sind. Ausgangsmaterialien zur Herstellung dieser NCO-Präpolymeren sind demzufolge

  • 1. beliebige organische Polyisocyanate, vorzugsweise Diisocyanate der Formel
    Figure imgb0059
    wobei Z" einen aliphatischen Kohlenwasserstoffrest mit 4 bis 12 Kohlenstoffatomen, einen cycloaliphatischen Kohlenwasserstoffrest mit 6 bis 15 Kohlenstoffatomen, einen aromatischen Kohlenwasserstoffrest mit 6 bis 15 Kohlenstoffatomen oder einen araliphatischen Kohlenwasserstoffrest mit 7 bis 15 Kohlenstoffatomen bedeutet. Beispiele derartiger bevorzugt einzusetzender Diisocyanate sind Tetramethylendiisocyanat, Hexamethylendiisocyanat, Dodecamethylendiisocyanat, 1,4-Diisocyanato-cyciohexan, 1-Isocyanato-3,3,5-trimethylisocyanatomethylcyclohexan, Isophorondiisocyanat, 4,4'-Diisocyanatodicyclohexylmethan, 4,4'-Diisocyanato-dicydohexylpropan-(2,2), 1,4-Diisocyanatobenzol, 2,4-Diisocyanatotoluol, 2,6-Diisocyanatotoluol, 4,4'-Diisocyanatodipheny)methan, 4,4'-Diisocyanato-diphenytpropan-(2,2), p-Xylylen-diisocyanat oder a,a,a',a'-Tetramethyl-m- oder -p-xylylen-diisocyanat, sowie aus diesen Verbindungen bestehende Gemische.
The preparation of the NCO prepolymers with chemically incorporated hydrophilic groups, which are preferably used in the process according to the invention, is carried out in analogy to the methods as mentioned in the literature references mentioned by way of example. Starting materials for the production of these NCO prepolymers are accordingly
  • 1. any organic polyisocyanates, preferably diisocyanates of the formula
    Figure imgb0059
     where Z "denotes an aliphatic hydrocarbon residue with 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon residue with 6 to 15 carbon atoms, an aromatic hydrocarbon residue with 6 to 15 carbon atoms or an araliphatic hydrocarbon residue with 7 to 15 carbon atoms. Examples of such preferred diisocyanates are tetramethylene diisocyanate, hexamethylene diisocyanate, Dodecamethylene diisocyanate, 1,4-diisocyanato-cyciohexane, 1-isocyanato-3,3,5-trimethylisocyanatomethylcyclohexane, isophorone diisocyanate, 4,4'-diisocyanatodicyclohexylmethane, 4,4'-diisocyanato-dicydohexylpropane- (2,2), 1,4- Diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodipheny) methane, 4,4'-diisocyanatodiphenytpropane- (2,2), p-xylylene diisocyanate or a, a, a ' , a'-Tetramethyl-m- or -p-xylylene diisocyanate, and mixtures consisting of these compounds.

Es ist selbstverständlich auch möglich, die in der Polyurethan-Chemie an sich bekannten höherfunktionellen Polyisocyanate oder auch an sich bekannte modifizierte, beispielsweise Carbodiimidgruppen, Allophanatgruppen, Isocyanuratgruppen, Urethangruppen und/oder Biuretgruppen aufweisende Polyisocyanate (mit)zuverwenden.It is of course also possible to use the polyisocyanates known per se in polyurethane chemistry, or else modified polyisocyanates (for example) containing carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups and / or biuret groups.

2. Beliebige organische Verbindungen mit mindestens zwei gegenüber Isocyanatgruppen reaktionsfähigen Gruppen, insbesondere insgesamt zwei Aminogruppen, Thiolgruppen, Carboxylgruppen und/oder Hydroxylgruppen aufweisende organische Verbindungen der Molekulargewichtsbereichs 62 bis 10000, vorzugsweise 100 bis 6 000 und insbesondere 500 bis 4 000. Bevorzugt werden die entsprechenden Dihydroxyverbindungen eingesetzt. Die Mitverwendung von im Sinne der Isocyanat-Polyadditionsreaktion tri- oder höher-funktionellen Verbindungen in geringen Anteilen zur Erzielung eines gewissen Verzweigungsgrades ist ebenso möglich wie die bereits erwähnte mögliche Mitverwendung von tri- oder höherfunktionellen Polyisocyanaten zum gleichen Zweck.2. Any organic compounds with at least two groups which are reactive toward isocyanate groups, in particular a total of two amino compounds, thiol groups, carboxyl groups and / or hydroxyl group-containing organic compounds of the molecular weight range 62 to 10,000, preferably 100 to 6,000 and in particular 500 to 4,000. The corresponding ones are preferred Dihydroxy compounds used. The use of tri-functional or higher-functional compounds in the sense of the isocyanate polyaddition reaction in small proportions to achieve a certain degree of branching is possible, as is the possible use of tri- or higher-functional polyisocyanates mentioned above for the same purpose.

Vorzugsweise einzusetzende Hydroxylverbindungen sind die in der Polyurethan-Chemie an sich bekannten Hydroxypolyester, Hydroxypolyether, Hydroxypolythioether, Hydroxypolyacetate, Hydroxypolycarbonate und/oder Hydroxypolyesteramide. Die in Frage kommenden Hydroxylgruppen aufweisenden Polyester sind z.B. Umsetzungsprodukte von mehrwertigen, vorzugsweise zweiwertigen und gegebenenfalls zusätzlich dreiwertigen Alkoholen mit mehrwertigen, vorzugsweise zweiwertigen, Carbonsäuren. Anstelle der freien Carbonsäuren können auch deren Anhydride oder Ester mit niederen Alkoholen zur Herstellung der Polyester verwendet werden. Die mehrwertigen Carbonsäuren können aliphatischer, cycloaliphatischer, aromatischer und/oder heterocyclischer Natur sein und gegebenenfalls, z.B. durch Halogenatome, substituiert und/oder ungesättigt sein. Als Beispiele hierfür seien genannt:Hydroxyl compounds to be preferably used are the hydroxypolyesters, hydroxypolyethers, hydroxypolythioethers, hydroxypolyacetates, hydroxypolycarbonates and / or hydroxypolyesteramides known per se in polyurethane chemistry. The hydroxyl group-containing polyesters are e.g. Reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polyhydric, preferably dihydric, carboxylic acids. Instead of the free carboxylic acids, their anhydrides or esters with lower alcohols can also be used to prepare the polyesters. The polyvalent carboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally, e.g. by halogen atoms, substituted and / or unsaturated. Examples include:

Bernsteinsäure, Adipinsäure, Korksäure, Azelainsäure, Sebacinsäure, Phthalsäure, Isophthalsäure, Trimellitsäure, Phthalsäureanhydrid, Tetrahydrophthalsäureanhydrid, Hexahydrophthalsäureanhydrid, Tetrachlorphthalsäureanhydrid, Endomethylentetrahydrophthalsäureanhydrid, Glutarsäureanhydrid, Maleinsäure, Maleinsäureanhydrid, Fumarsäure, dimere un trimere Fettsäuren wie Ölsäure, gegebenenfalls in Mischung mit monomeren Fettsäuren, Terephthalsäuredimethylester, Terephthalsäure-bis-glykolester. Als mehrwertige Alkohole kommen z.B. Ethylenglykol, Propylenglykol-(1,2) und -(1,3), Butylenglykol-(1,4) und -(2,3), Hexandiol-(1,6), Octandiol-(1,8), Neopentylglykol, 1,4-Bis-hydroxymethylcyclohexan, 2-Methyl-1,3-propandiol, Glycerin, Trimethylolpropan, Hexantriol-(1,2,6), Butantriol-(1,2,4), Trimethylolether, Pentaerythrit, Chinit, Mannit und Sorbit, Methylglykosid, ferner Diethylenglykol, Triethylenglykol, Tetraethylenglykol, Polyethylenglykole, Dipropylenglykol, Polypropylenglykole, Dibutylenglykol und Polybutylenglykole in Frage. Die Polyester können anteilig endständige Carboxylgruppen aufweisen. Auch Polyester aus Lactonen, z.B. E-Caprolacton oder Hydroxycarbonsäuren, z.B. w-Hydroxycapronsäure, sind einsetzbar.Succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimeric un trimeric fatty acids such as oleic acid, optionally mixed with monomeric fatty acids, terephthalic acid dimethyl ester, Terephthalic acid bis-glycol ester. Polyhydric alcohols include, for example, ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol (1,4) and - (2,3), hexanediol (1,6), octanediol (1, 8), neopentyl glycol, 1,4-bis-hydroxymethylcyclohexane, 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, hexanetriol (1,2,6), butanetriol (1,2,4), trimethylol ether, pentaerythritol , Quinite, mannitol and sorbitol, methyl glycoside, also diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycol in question. The polyesters can have a proportion of terminal carboxyl groups. Polyesters from lactones, for example E- caprolactone or hydroxycarboxylic acids, for example w-hydroxycaproic acid, can also be used.

Die ebenfalls in Frage kommenden, vorzugsweise zwei Hydroxylgruppen aufweisenden Polyether sind solche der an sich bekannten Art und werden z.B. durch Polymerisation von Epoxiden wie Ethylenoxid, Propylenoxid, Butylenoxid, Tetrahydrofuran, Styroloxid oder Epichlorhydrin mit sich selbst, z.B. in Gegenwart von BF3 oder durch Anlagerung dieser Epoxide, gegebenenfalls im Gemisch oder nacheinander, an Startkomponenten mit reaktionsfähigen Wasserstoffatomen wie Alkohole und Amine, z.B. Wasser, Ethylenglykol, Propylenglykol-(1,3) oder -(1,2), 4,4'-Dihydroxydiphenylpropan, Anilin, hergestellt.The polyethers which are also suitable, preferably having two hydroxyl groups, are those of the type known per se and are obtained, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, for example in the presence of BF 3 or by addition these epoxides, optionally in a mixture or in succession, on starting components with reactive hydrogen atoms such as alcohols and amines, for example water, ethylene glycol, propylene glycol (1,3) or - (1,2), 4,4'-dihydroxydiphenylpropane, aniline.

Auch durch Vinylpolymerisate modifizierte Polyether, wie sie z.B. durch Polymerisation von Styrol/ Acrylnitril in Gegenwart von Polyethern entstehen (US-A-3 383 351, US-A-3 304 273, US-A-3 523 093, US-A-3 110695, DE-C-1 152 536), sind ebenfalls geeignet. Die anteilig gegebenenfalls mitzuverwendenden höherfunktionellen Polyether entstehen in analoger Weise durch an sich bekannte Alkoxylierung von höherfunktionellen Startermolekülen z.B. Ammoniak, Ethanolamin, Ethylendiamin oder Sukrose.Also polyethers modified by vinyl polymers, e.g. by polymerization of styrene / acrylonitrile in the presence of polyethers (US-A-3 383 351, US-A-3 304 273, US-A-3 523 093, US-A-3 110695, DE-C-1 152 536 ) are also suitable. The proportionally higher-functionality polyethers to be used, if appropriate, are formed in an analogous manner by alkoxylation of higher-functionality starter molecules known per se, e.g. Ammonia, ethanolamine, ethylenediamine or sucrose.

Unter den Hydroxypolythioethern seien insbesondere die Kondensationsprodukte von Thiodiglykol mit sich selbst und/oder mit anderen Glykolen, Dicarbonsäuren, Formaldehyd, Aminocarbonsäuren oder Aminoalkoholen angeführt. Je nach den CO-Komponenten handelt es sich bei den Produkten um Polythiomischether, Polythioetherester, Polythioetheresteramide.Among the hydroxypolythioethers, the condensation products of thiodiglycol with itself and / or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols should be mentioned in particular. Depending on the CO components, the products are polythio mixed ethers, polythioether esters, polythioether ester amides.

Als Hydroxypolyacetale kommen z.B. die aus Glykolen, wie Diethylenglykol, Triethylenglykol, 4,4'-Diethoxy-diphenyldimethylmethan, Hexandiol und Formaldehyd herstellbaren Verbindungen in Frage. Auch durch Polymerisation cyclischer Acetale lassen sich geeignete Polyacetale herstellen.As hydroxypolyacetals, e.g. the compounds which can be prepared from glycols, such as diethylene glycol, triethylene glycol, 4,4'-diethoxy-diphenyldimethylmethane, hexanediol and formaldehyde. Suitable polyacetals can also be prepared by polymerizing cyclic acetals.

Als Hydroxylgruppen aufweisende Polycarbonate kommen solche der an sich bekannten Art in Betracht, die z.B. durch Umsetzung von Diolen wie Propandiol-(1,3), Butandiol-(1,4) und/oder Hexandiol-(1,6), Diethylenglykol, Triethylenglykol, Tetraethylenglykol mit Diarylcarbonaten, z.B. Diphenylcarbonat oder Phosgen, hergestellt werden können.Suitable polycarbonates containing hydroxyl groups are those of the type known per se, which e.g. by reacting diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6), diethylene glycol, triethylene glycol, tetraethylene glycol with diaryl carbonates, e.g. Diphenyl carbonate or phosgene can be produced.

Zu den Hydroxylgruppen enthaltenden Polyesteramiden und Polyamiden zählen z.B. die aus mehrwertigen gesättigten und ungesättigten Carbonsäuren bzw. deren Anhydriden und mehrwertigen gesättigten und ungesättigten Aminoalkohlen, Diaminen, Polyaminen und ihren Mischungen gewonenen, vorwiegend linearen Kondensate. Auch bereits Urethan- oder Harnstoffgruppen enthaltende Polyhydroxylverbindungen sind verwendbar.The hydroxyl group-containing polyester amides and polyamides include e.g. the predominantly linear condensates obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines and their mixtures. Polyhydroxyl compounds already containing urethane or urea groups can also be used.

Auch niedermolekulare Polyole können (mit)verwendet werden, wie z.B. Ethandiol, Proparidiol-1,2 und -1,3, Butandiol-1,4 und -1,3, Pentandiole, Hexandiole, Trimethylolpropan, Hexantriole, Glycerin und Pentaerythrit.Low molecular weight polyols can also be used, e.g. Ethanediol, 1,2-propanediol and 1,3, 1,4-butanediol and 1,3, pentanediols, hexanediols, trimethylolpropane, hexanetriols, glycerol and pentaerythritol.

Vertreter der erwähnten Polyisocyanate wie auch der Polyhydroxylverbindungen sind z.B. in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology", verfaßt von Saunders-Frisch, Interscience Publishers, New York, London, Band, I, 1962, Seiten 32-42 und Seiten 44-54 und Band 11, 1964, Seiten 5―6 und 198-199, sowie im Kunststoff-Handbuch, Band VII, Vieweg-Höchtlen, Carl-Hanser-Verlag, München, 1966, z.B. auf den Seiten 45 bis 71, beschrieben.Representatives of the polyisocyanates mentioned and also of the polyhydroxyl compounds are described, for example, in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology", written by Saunders-Frisch, Interscience Publishers, New York, London, Volume, I, 1962, pages 32-42 and pages 44-54 and volume 11, 1964, Pages 5―6 and 198-199, as well as in the Plastics Manual, Volume VII, Vieweg-Höchtlen, Carl-Hanser-Verlag, Munich, 1966, e.g. on pages 45 to 71.

3. Chemisch fixierte hydrophile Gruppen aufweisende, vorzugsweise im Sinne der Isocyanat-Additionsreaktionen mono- und insbesondere difunktionelle Aufbaukomponenten der beispielhaft in den obengenannten Literaturstellen bezüglich der Herstellung von wäßrigen Polyurethandispersionen oder -lösungen beschriebenen Art, d.h. beispielsweise ionische bzw. potentielle ionische Gruppen aufweisende Diisocyanate, Diamine oder Dihydroxyverbindungen bzw. Polyethylenoxid-Einheiten aufweisende Diisocyanate oder Glykole. Zu den bevorzugten hydrophil modifizierten Aufbaukomponenten gehören insbesondere die Sulfonatgruppen aufweisenden aliphatischen Diole gemäß DE-A-2446440, die kationischen oder auch anionischen einbaufähigen inneren Emulgatoren gemäß DE-A-26 51 506 und auch die dort beschriebenen monofunktionellen einbaufähigen Polyether. Bei der Herstellung der NCO-Präpolymeren nach an sich bekannten Prinzipien des Standes der Tecknik werden die Reaktionspartner im allgemeinen in solchen Mengenverhältnissen eingesetzt, die einem Verhältnis von Isocyanatgruppen zu gegenüber NCO-reaktiven Wasserstoffatomen, vorzugsweise aus Hydroxylgruppen, von 1,05 bis 10, vorzugsweise von 1,1 bis 3, entsprechen.3. Chemically fixed hydrophilic groups, preferably in the sense of the isocyanate addition reactions, mono- and in particular difunctional structural components of the type described by way of example in the literature references mentioned above with regard to the preparation of aqueous polyurethane dispersions or solutions, i.e. for example, diisocyanates, diamines or dihydroxy compounds, or diisocyanates or glycols containing ionic or potential ionic groups, or polyethylene oxide units. The preferred hydrophilically modified structural components include, in particular, the sulfonate group-containing aliphatic diols according to DE-A-2446440, the cationic or also anionic internal emulsifiers according to DE-A-26 51 506 and also the monofunctional built-in polyethers described there. In the preparation of the NCO prepolymers according to principles known per se from the state of the art in Tecknik, the reactants are generally used in such proportions that a ratio of isocyanate groups to hydrogen atoms which are reactive towards NCO, preferably from hydroxyl groups, is preferably from 1.05 to 10 from 1.1 to 3.

Die Reihenfolge der Zugabe der einzelnen Reaktionspartner ist hierbei weitgehend beliebig. Man kann sowohl die Hydroxylverbindungen abmischen und dazu das Polyisocyanat zufügen oder auch zur Polyisocyanatkomponente das Gemisch der Hydroxylverbindungen oder die einzelnen Hydroxylverbindungen nach und nach eintragen.The order in which the individual reactants are added is largely arbitrary. You can either mix the hydroxyl compounds and add the polyisocyanate, or you can gradually add the mixture of hydroxyl compounds or the individual hydroxyl compounds to the polyisocyanate component.

Die Herstellung der NCO-Präpolymere erfolgt vorzugsweise in der Schmelze bei 30 bis 190°C, vorzugsweise bei 50 bis 120°C. Die Herstellung der Präpolymere kann selbstverständlich auch in Gegenwart von organischen Lösungsmitteln erfolgen, obwohl ein wesentlicher Vorteil gerade in dem möglichen Verzicht auf derartige Lösungsmittel zu sehen ist. Geeignete Lösungsmittel, die z.B. zur Viskositätserniedrigung besonders hochschmelzender Präpolymerer im Mengen bis zu 30 Gew.-%, bezogen auf Feststoff, eingesetzt werden können, wären z.B. Aceton, Methylethylketon, Essigsäureethylester, Dimethylformamid, Cyclohexanon, Dioxan, Glykoldimethylether, Glykoletheracetate.The NCO prepolymers are preferably produced in the melt at 30 to 190 ° C., preferably at 50 to 120 ° C. The preparation of the prepolymers can of course also be carried out in the presence of organic solvents, although a major advantage can be seen in the fact that such solvents are not required. Suitable solvents, e.g. to lower the viscosity of particularly high-melting prepolymers in amounts of up to 30% by weight, based on solids, would be, for example Acetone, methyl ethyl ketone, ethyl acetate, dimethylformamide, cyclohexanone, dioxane, glycol dimethyl ether, glycol ether acetates.

Die Art und Mengenverhältnisse der bei der Herstellung der NCO-Präpolymeren eingesetzten Ausgangsmaterialien werden im übrigen vorzugsweise so gewählt, daß die NCO-Präpolymeren

  • a) eine mittlere NCO-Funktionalität von 1,8 bis 2,2, vorzugsweise von etwa 2,
  • b) einen Gehalt an kationischen oder anionischen eingebauten Gruppen von 0 bis 100, vorzugsweise 0,1 bis 100 und insbesondere 0,5 bis 50 Milli-Äquivalent pro 100 g Feststoff,
  • c) einen Gehalt an seitenständig, endständig und/oder innerhalb der Hauptkette eingebauten, innerhalb eines Polyethersegments vorliegenden Ethylenoxid-Einheiten von 0 bis 30, vorzugsweise 0,5 bis 30 und insbesondere 1 bis 20 Gew.-%, bezogen auf das Gesamtgewicht des Präpolymeren und
  • d) ein mittleres Molekulargewicht von 500 bis 10 000, vorzugsweise 800 bis 4 000 aufweisen.
The nature and proportions of the starting materials used in the preparation of the NCO prepolymers are preferably chosen so that the NCO prepolymers
  • a) an average NCO functionality of 1.8 to 2.2, preferably of about 2,
  • b) a content of cationic or anionic built-in groups of 0 to 100, preferably 0.1 to 100 and in particular 0.5 to 50 milliequivalents per 100 g of solid,
  • c) a content of laterally, terminally and / or within the main chain, ethylene oxide units present within a polyether segment of 0 to 30, preferably 0.5 to 30 and in particular 1 to 20% by weight, based on the total weight of the prepolymer and
  • d) have an average molecular weight of 500 to 10,000, preferably 800 to 4,000.

Zu den bevorzugten NCO-Präpolymeren gehören, wie bereits dargelegt, solche, welche entweder ionische Gruppen der unter b) genannten Art, d.h. insbesondere -COO°, -S03° oder

Figure imgb0060
oder nichtionische Gruppen der unter c) genannten Art oder sowohl ionische als auch nichtionische Gruppen der genannten Art aufweisen. Es ist jedoch auch möglich, beim erfindungsgemäßen Verfahren NCO-Präpolymere einzusetzen, bei deren Herstellung keine der unter 3. genannten hydrophilen Aufbaukomponenten mitverwendet wurden, bei denen der Gehalt der oben unter b) bzw. c) genannten Gruppen somit 0 beträgt.As already stated, the preferred NCO prepolymers include those which are either ionic groups of the type mentioned under b), ie in particular -COO °, -S0 3 ° or
Figure imgb0060
 or have nonionic groups of the type mentioned under c) or both ionic and nonionic groups of the type mentioned. However, it is also possible to use NCO prepolymers in the process according to the invention, in the production of which none of the hydrophilic structural components mentioned under 3. were used, in which the content of the groups mentioned under b) or c) is therefore 0.

Zur Herstellung der erfindungsgemäßen Polyadditions- bzw. Polykondensationsprodukte werden Dihydroxy- oder Diaminoverbindungen der Formel 111 und gegebenenfalls weitere organische Verbindungen mit mindestens zwei gegenüber Isocyanatgruppen reaktionsfähigen Gruppen mit organischen Polyisocyanaten umgesetzt. Die Reaktion kann dabei so geführt werden, daß zunächst durch Umsetzung des Polyisocyanates mit einer ersten reaktionsfähigen Verbindung ein bi- oder polyfunktionelles NCO-Präpolymer hergestellt wird, das dann mit einer zweiten und gegebenenfalls weiteren reaktionsfähigen Verbindung weiter umgesetzt wird. Die fotografisch nützliche Verbindung der Formel 111 kann dabei als erste, als zweite oder auch als weitere reaktionsfähige Verbindung zum Einsatz gelangen. Es ist aber auch möglich das Polyisocyanat mit einem Gemisch der reaktionsfähigen Verbindungen, das unter anderem auch die niedermolekulare fotografisch nützliche Verbindung der Formel 111 enthält, umzusetzen. Die Umsetzungsbedingungen sind dem Fachmann geläufig. Es handelt sich um Bedingungen, unter denen üblicherweise Polyurethane bzw. Polyharnstoffe hergestellt werden. Bevorzugt werden solche Verfahren angewendet, bei denen das Polyadditions- bzw. Polykondensationsprodukt direkt in Form einer Dispersion bzw. eines Latex anfallen.To produce the polyaddition or polycondensation products according to the invention, dihydroxy or diamino compounds of the formula III and, if appropriate, further organic compounds having at least two groups which are reactive toward isocyanate groups are reacted with organic polyisocyanates. The reaction can be carried out by first producing a bi- or polyfunctional NCO prepolymer by reacting the polyisocyanate with a first reactive compound, which is then reacted further with a second and optionally further reactive compound. The photographically useful compound of formula 111 can be used as the first, second or also as a further reactive compound. However, it is also possible to react the polyisocyanate with a mixture of the reactive compounds which also contains, inter alia, the low molecular weight photographically useful compound of the formula III. The reaction conditions are familiar to the person skilled in the art. These are conditions under which polyurethanes or polyureas are usually produced. Those processes are preferably used in which the polyaddition or polycondensation product is obtained directly in the form of a dispersion or a latex.

Anschließend wird das Reaktionsgemisch mit Wasser vermischt zur Herstellung der wäßrigen Lösung bzw. Dispersion. Man benutzt hierfür zweckmäßigerweise nur so viel Wasser, daß die Lösung bzw. Dispersion einen möglichst hohen Festkörperanteil aufweist. Vorzugsweise lassen sich Lösungen bzw. Dispersionen mit 30 bis 60 Gew.-% Feststoffgehalt sehr gut herstellen. Weiteres Verdünnen mit Wasser ist ohne weiteres möglich. Das Wasser wird vorzugsweise in einem Guß oder je nach Belieben nach und nach zugegeben. Die Vermischung des Reaktionsgemisches mit Wasser kann aber auch so erfolgen, daß des Gemisch in die wäßrige Phase eingetragen wird. Man benutzt beispielsweise Wasser von 0 bis 90°C, vorzugsweise von 15 bis 60°C.The reaction mixture is then mixed with water to produce the aqueous solution or dispersion. Expediently, only enough water is used for this that the solution or dispersion has as high a solids content as possible. Solutions or dispersions with a solids content of 30 to 60% by weight can preferably be prepared very well. Further dilution with water is easily possible. The water is preferably added in one pour or gradually as desired. However, the reaction mixture can also be mixed with water in such a way that the mixture is introduced into the aqueous phase. For example, water from 0 to 90 ° C, preferably from 15 to 60 ° C, is used.

Die entstehenden Dispersionen sind sehr feinteilig, die Teilchen haben vorzugsweise eine Größe von 20 bis 200 nm, können natürlich auch größer sein.The resulting dispersions are very fine, the particles preferably have a size of 20 to 200 nm, can of course also be larger.

Die Frage, ob beim erfindungsgemäßen Verfahren Lösungen oder Dispersionen der Polyurethane bzw. Polyharnstoffe in Wasser erhalten werden, ist vor allem vom Molekulargewicht und der Hydrophilie der gelösten bzw. dispergierten Teilchen abhängig, welche ihrerseits durch geeignete Wahl von Art und Mengenverhältnis der Ausgangsmaterialien, insbesondere bei der Herstellung der NCO-Präpolymeren nach den bekannten Prinzipien der Polyurethan-Chemie eingestellt werden können. So führt beispielsweise die Verwendung von einem NCO-Präpolymeren mit der geringfügig unter 2 liegenden mittleren NCO-Funktionalität zu einem Abbruch der Polyadditionsreaktion, bevor allzu hohe Molekulargewichte erreicht sind.The question of whether solutions or dispersions of the polyurethanes or polyureas in water are obtained in the process according to the invention is primarily dependent on the molecular weight and the hydrophilicity of the dissolved or dispersed particles, which in turn depends on a suitable choice of the type and quantitative ratio of the starting materials, in particular for the production of the NCO - prepolymers can be adjusted according to the known principles of polyurethane chemistry. For example, the use of an NCO prepolymer with the mean NCO functionality slightly below 2 leads to the polyaddition reaction being terminated before excessively high molecular weights are reached.

Anstelle mit einer einzigen niedermolekularen fotografisch nützlichen Verbindung gemäß Formel 111 können die erfindungsgemäßen Polyadditions- bzw. Polykondensationsprodukte auch mit einer Mehrzahl solcher fotografisch nützlichen Verbindungen gemäß Formel 111 hergestellt werden, wobei sich diese verschiedenen Ausgangsmaterialien gemäß Formel 111 in der Bedeutung von Q unterscheiden können. Auf diese Weise ist es möglich unterschiedliche fotografische Funktionen (Q) in einem einzigen Polymer zusammenzufassen ohne daß man hinsichtlich der Stöchiometrie irgendwelchen Beschränkungen unterworfen ist. Beispielsweise ist es möglich Kupplereinheiten, die bei Farbkupplung unterschiedliche Farbstoffe liefern, in dem Polymer zusammenzufassen um auf diese Weise bei Farbkupplung eine Mischfarbe zu erzeugen. Desweiteren ist es möglich zusätzlich zu Farbkupplereinheiten weitere Struktureinheiten einer anderen Funktion, z.B. Weißkuppler- oder DIR-Kupplereinheiten in ein Polymer einzubauen. Schließlich bietet es sich auch an beispielsweise Struktureinheiten mit reduzierbaren Farbabspaltern und Struktureinheiten mit Elektronendonorvorläuferresten (verkappte Reduktionsmittel) in einem Polymer zusammenzufassen.Instead of using a single low molecular weight photographically useful compound according to formula 111, the polyaddition or polycondensation products according to the invention can also be prepared with a plurality of such photographically useful compounds according to formula 111, it being possible for these different starting materials according to formula 111 to differ in the meaning of Q. In this way it is possible to combine different photographic functions (Q) in a single polymer without any restrictions in terms of stoichiometry. For example, it is possible to combine coupler units which supply different dyes in the case of color coupling in the polymer in order in this way to produce a mixed color in the case of color coupling. In addition to color coupler units, it is also possible to use other structural units of another function, e.g. Install white coupler or DIR coupler units in a polymer. Finally, it is also possible to combine structural units with reducible color releasers and structural units with electron donor precursor residues (masked reducing agents) in one polymer.

Nach dem erfindungsgemäßen Polyadditions- bzw. Polykondensationsverfahren werden Latices von fotografisch nützlichen Verbindungen mit geringer Teilchengröße und hoher Dispersionsstabilität erhalten.According to the polyaddition or polycondensation process according to the invention, latices of photographically useful compounds with a small particle size and high dispersion stability are obtained.

Bei der Herstellung des fotografischen Aufzeichnungsmaterials können die Polyadditions- bzw. Polykondensationsprodukte der vorliegenden Erfindung in bekannter Weise in die Gießlösung der Silberhalogenidemulsionsschichten oder anderer Kolloidschichten eingearbeitet werden, indem sie vorzugsweise in Form von wäßrigen Dispersionen, wie sie bei der Herstellung erhalten werden können, gegebenenfalls in Anwesenheit eines Netz- oder Dispergiermittels zu einer hydrophilen Kolloidlösung zugefügt werden. Die hydrophile Gießlösung kann selbstverständlich neben dem Bindemittel andere übliche Zusätze enthalten.In the preparation of the photographic recording material, the polyaddition or polycondensation products of the present invention can be incorporated into the casting solution of the silver halide emulsion layers or other colloid layers in a known manner, preferably by optionally in the form of aqueous dispersions, as can be obtained in the preparation, in The presence of a wetting or dispersing agent can be added to a hydrophilic colloid solution. The hydrophilic casting solution can of course contain other conventional additives in addition to the binder.

Die wäßrige Dispersion braucht nicht direkt in die Gießlösung für die Silberhalogenidemulsionsschicht oder eine andere wasserdurchlässige Schicht dispergiert zu werden; sie kann vielmehr auch vorteilhaft zuerst in einer wäßrigen nicht-lichtempfindlichen Lösung eines hydrophilen Kolloids dispergiert werden, worauf das erhaltene Gemisch gegebenenfalls nach Entfernung der verwendeten organischen Lösungsmittel mit der Gießlösung für die lichtempfindliche Silberhalogenidemulsionsschicht oder einer anderen wasserdurchlässigen Schicht vor dem Auftragen vermischt wird.The aqueous dispersion need not be directly dispersed in the casting solution for the silver halide emulsion layer or other water permeable layer; Rather, it can also be advantageously first dispersed in an aqueous, non-photosensitive solution of a hydrophilic colloid, whereupon the mixture obtained, after removal of the organic solvents used, may be mixed with the casting solution for the photosensitive silver halide emulsion layer or another water-permeable layer before application.

Als lichtempfindliche Silberhalogenidemulsionen eignen sich Emulsionen von Silberhalogenid, Silberbromid oder Gemische davon, evtl. mit einem Geringen Gehalt an Siliodid bis zu 10 mol-% in einem der üblicherweise verwendeten hydrophilen Bindemittel. Als Bindemittel für die fotografischen Schichten wird vorzugsweise Gelatine verwendet. Diese kann jedoch ganz oder teilweise durch andere natürliche oder synthetische Bindemittel ersetzt werden.Suitable light-sensitive silver halide emulsions are emulsions of silver halide, silver bromide or mixtures thereof, possibly with a low siliodide content of up to 10 mol% in one of the commonly used hydrophilic binders. Gelatin is preferably used as a binder for the photographic layers. However, this can be replaced in whole or in part by other natural or synthetic binders.

Die Emulsionen können in der üblichen Weise chemisch oder spektral sensibilisiert sein und die Emulsionsschichten wie auch andere nicht-lichtempfindliche Schichten können in der üblichen Weise mit bekannten Härtungsmitteln gehärtet sein.The emulsions can be chemically or spectrally sensitized in the usual way and the emulsion layers as well as other non-light-sensitive layers can be hardened in the usual way with known hardening agents.

Die Schichten, die die erfindungsgemäßen Polyadditions- bzw. Polykondensationsprodukte enthalten, wie auch andere Schichten des fotografischen Aufzeichnungsmaterials, können in üblicher Weise weitere Zusätze enthalten, z.B. Lichtschutzmittel, UV-Absorber, Formalinfänger, Reduktionsmittel, Kuppler und dergleichen, wobei die genannten Zusätze in polymerer Form oder in niedermolekularer Form vorliegen können.The layers which contain the polyaddition or polycondensation products according to the invention, as well as other layers of the photographic recording material, can contain further additives in the usual way, e.g. Light stabilizers, UV absorbers, formalin scavengers, reducing agents, couplers and the like, it being possible for the additives mentioned to be present in polymeric form or in low molecular weight form.

Für die Herstellung farbfotografischer Bilder enthält das erfindungsgemäße fotografische Aufzeichnungsmaterial in der Regel mindestens drei Silberhalogenidemulsionsschichten und diesen zugeordnete Farbkuppler, wobei in diesem Fall mindestens einer Silberhalogenidemulsionsschicht der entsprechende Farbkuppler in Form einer der erfindungsgemäßen Polyadditions- bzw. Polykondensationsprodukte zugeordnet ist. Die entsprechende Verbindung kann hierbei in der Silberhalogenidemulsionsschicht selbst oder auch in einer hierzu benachbarten nicht lichtempfindlichen Bindemittelschicht enthalten sein. Entwickelt wird in diesem Fall mit einem Farbenwickler.For the production of color photographic images, the photographic recording material according to the invention generally contains at least three silver halide emulsion layers and associated color couplers, in which case at least one silver halide emulsion layer is assigned the corresponding color coupler in the form of one of the polyaddition or polycondensation products according to the invention. The corresponding compound can be contained in the silver halide emulsion layer itself or in a non-light-sensitive binder layer adjacent to it. In this case, development is carried out with a paint roller.

Als Farbentwicklerverbindung lassen sich sämtliche Entwicklerverbindungen verwenden, die die Fähigkeit besitzen in Form ihres Oxidationsproduktes mit Farbkupplern zu Azomethinfarbstoffen zu reagieren. Geeignete Farbenwicklerverbindungen sind aromatische mindestens eine primäre Aminogruppe enthaltende Verbindungen vom p-Phenylendiamintyp, beispielsweise, N,N-Dialkyl-p-phenylendiamine, wie N,N-Diethyl-p-phenylendiamin, 1-(N-ethyl-N-methylsulfonamidoethyl)-3-methyl-p-phenylendiamin, 1-(N-ethyl-N-hydroxyethyl-3-methyl-p-phenylendiamin) und 1-(N-ethyl-N-methoxyethyl)-3-methyl- p-phenylendiamin. Andere Silberhalogenidentwicklerverbindungen können ebenfalls zur Anwendung gelangen, falls die Farbbilderzeugung nicht auf der chromogenen Entwicklung beruht.All developer compounds which have the ability in the form of their oxidation product to react with color couplers to form azomethine dyes can be used as the color developer compound. Suitable color developer compounds are aromatic at least one primary amino group-containing compounds of the p-phenylenediamine type, for example, N, N-dialkyl-p-phenylenediamines, such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methylsulfonamidoethyl) -3-methyl-p-phenylenediamine , 1- (N-ethyl-N-hydroxyethyl-3-methyl-p-phenylenediamine) and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine. Other silver halide developer compounds can also be used if the color imaging is not based on chromogenic development.

Beispiel 1example 1 Polyurethan-Gelbkupplerlatex APolyurethane yellow coupler latex A

Eine Mischung aus 68 g Hexandiol-Neopentylglykol-Polyadipat (MG 1700), 131 g Verbindung M-1 und 50 ml trockenem Toluol werden auf ca. 100°C erwärmt. Bei dieser Temperatur tropft man zügig eine Mischung aus 37 g lsophorondiisocyanat und 28 g 1,6-Hexamethyiendiisocyanat zu. Die klare Lösung wird 3 h bei 105―110°C gehalten. Die NCO-Titration ergibt nach Verdünnen mit 720 ml Aceton einen Gehalt von 3,3% NCO (ber. 3,7% NCO).A mixture of 68 g of hexanediol-neopentyl glycol polyadipate (MW 1700), 131 g of compound M-1 and 50 ml of dry toluene are heated to approximately 100 ° C. A mixture of 37 g of isophorone diisocyanate and 28 g of 1,6-hexamethylene diisocyanate is rapidly added dropwise at this temperature. The clear solution is kept at 105-110 ° C for 3 h. After dilution with 720 ml acetone, the NCO titration gives a content of 3.3% NCO (calc. 3.7% NCO).

397 g dieser Lösung werden bei 50°C mit einer Mischung aus 18,4 g (50 mmol) einer wäßrigen Lösung des Natriumsalzes von β'-Aminoethyl-β-aminoethansulfonsäure und 25 ml Wasser versetzt. Nach ca. 10 min dispergiert man mit 310 ml entsalztem Wasser und befreit im Vakuum vom Lösungsmittel.397 g of this solution are mixed at 50 ° C. with a mixture of 18.4 g (50 mmol) of an aqueous solution of the sodium salt of β'-aminoethyl-β-aminoethanesulfonic acid and 25 ml of water. After approx. 10 min, the mixture is dispersed with 310 ml of deionized water and the solvent is removed in vacuo.

Man erhält eine sehr feinteilige wäßrige Dispersion des polyurethanharnstoffmodifizierten Kupplers mit folgenden Daten:

Figure imgb0061
A very finely divided aqueous dispersion of the polyurethane-urea-modified coupler is obtained with the following data:
Figure imgb0061

Beispiel 2Example 2 Polyurethan-Gelbkupplerlatex BPolyurethane yellow coupler latex B

Man arbeitet völlig analog Beispiel 1, verwendet aber nunmehr lediglich 15,9 g (43 mmol) des Natriumsalzes von β'-Aminoethyl-β-aminoethansulfonsäure.The procedure is completely analogous to Example 1, but now only 15.9 g (43 mmol) of the sodium salt of β'-aminoethyl-β-aminoethanesulfonic acid are used.

Die Aufarbeitung gemäß Beispiel 1 ergibt eine stabile Dispersion mit folgenden Daten:

Figure imgb0062
Working up according to Example 1 gives a stable dispersion with the following data:
Figure imgb0062

Beispiel 3Example 3 Polyurethan-Purpurkupplerlatex CPolyurethane purple coupler latex C

Zu einer Mischung aus 85 g (0,05 mol) Hexandiol-Neopentylglykol-Polyadipat, 125 g der Verbindung M-12 und 500 ml trockenem Toluol tropft man bei 105°C zügig eine Mischung aus 47,5 g Isophorondiisocyanat und 37,6 g 1,6-Hexamethylendiisocyanat. Nach 2-stündigem Erwärmen auf 105-110°C wird das Toluol abdestilliert. Man löst in 689 g Aceton. Der NCO-Gehalt wird zu 2,7% bestimmt.A mixture of 47.5 g of isophorone diisocyanate and 37.6 g is quickly added dropwise at 105 ° C. to a mixture of 85 g (0.05 mol) of hexanediol-neopentyl glycol polyadipate, 125 g of the compound M-12 and 500 ml of dry toluene 1,6-hexamethylene diisocyanate. After heating to 105-110 ° C for 2 hours, the toluene is distilled off. It is dissolved in 689 g of acetone. The NCO content is determined to be 2.7%.

Die acetonische Lösung wird mit einer Mischung aus 50 ml Wasser und 40,1 g einer 51,6 %igen wäßrigen Lösung des Natriumsalzes der β'-Aminoethyl-β-aminoethansulfonsäure versetzt. Nach 10 min bei 50°C dispergiert man mit 675 ml entsalztem Wasser und befreit im Vakuum vom Lösungsmittel.A mixture of 50 ml of water and 40.1 g of a 51.6% strength aqueous solution of the sodium salt of β'-aminoethyl-β-aminoethanesulfonic acid is added to the acetone solution. After 10 min at 50 ° C., the mixture is dispersed with 675 ml of demineralized water and the solvent is removed in vacuo.

Man erhält eine Dispersion mit folgenden Daten:

Figure imgb0063
A dispersion is obtained with the following data:
Figure imgb0063

Beispiel 4Example 4 Polyurethan-Purpurkupplerlatex DPolyurethane purple coupler latex D

Unter Ausschluß von Feuchtigkeit werden 11 g Isophorondiisocyanat und 33,5 g einer NCO-Präpolymers aus Hexandiol-Neophentylglykol-Polyadipat (Molekulargewicht 1700) und 1,6-Hexamethylendiisocyanat (NCO-Gehalt des Präpolymers 2,7%) in 300 g trockenem 3-Pentanon gelöst. Dann gibt man eine Lösung von 16,5 g Kupplerdiol M-12 gelöst in 250 g 3-Pentanon und rührt 4 h bei Siedetemperatur. Dann gibt man 7,2 g einer 49,3 %igen wäßrigen Lösung von (ß'-Aminoethyl)-ß-aminoethansulfonsäure-Na-Salz zur der Reaktionslösung und tropft nach 15 min 150 g Wasser zu. Nach Abdestillieren des Lösungsmittels und Dialyse wird ein feinteiliger Polyurethan Kupplerlatex mit einem Äquivalentmolekulargewicht von 1587 erhalten.Excluding moisture, 11 g of isophorone diisocyanate and 33.5 g of an NCO prepolymer made from hexanediol-neophentyl glycol polyadipate (molecular weight 1700) and 1,6-hexamethylene diisocyanate (NCO content of the prepolymer 2.7%) are mixed in 300 g dry 3- Pentanon solved. Then you give a solution of 16.5 g of coupler diol M-12 dissolved in 250 g of 3-pentanone and stirred at boiling temperature for 4 h. Then 7.2 g of a 49.3% strength aqueous solution of (β'-aminoethyl) -β-aminoethanesulfonic acid Na salt are added to the reaction solution and 150 g of water are added dropwise after 15 minutes. After distilling off the solvent and dialysis, a finely divided polyurethane coupler latex with an equivalent molecular weight of 1587 is obtained.

Beispiel 5Example 5 Polyurethan-Purpurkupplerlatex EPolyurethane purple coupler latex E

Man verfährt wie in Beispiel 4 beschrieben, setzt aber an Stelle des Kupplerdiols M-12 22 g des Kupplerdiols M-13 ein. Es wird ein feinteiliger Polyurethan-Purpurkupplerlatex mit einem Äquivalentmolekulargewicht von 1724 erhalten.The procedure is as described in Example 4, but 22 g of coupler diol M-13 are used in place of coupler diol M-12. A finely divided polyurethane magenta coupler latex with an equivalent molecular weight of 1724 is obtained.

Beispiel 6Example 6 Polyurethan-Gelbkupplerlatex FPolyurethane yellow coupler latex F

Unter Feuchtigkeitsausschluß werden 1,8 g Isophorondiisocyanat und 6,7 g der in Beispiel 4 beschriebenen Präpolymeren in 60 g 3-Pentanon gelöst. Dann gibt man bei Raumtemperatur 6 g Kupplerdiol M-4 gelöst in 50 g 3-Pentanon und rührt dann 3 h bei Siedetemperatur. Anschließend gibt man 1,8 g einer 49,3 %igen wäßrigen Lösung des Natriumsalzes der β'-Aminoethyl-β-aminoethansulfonsäure zu der Reaktionslösung und tropft nach 15 min innerhalb von 3 min 30 g Wasser zu. Nach Abdestillieren des Lösungsmittels am Reaktionsverdampfer und Dialyse wird ein feinteiliger Polyurethan-Gelbkupplerlatex mit einem Äquivalentmolekulargewicht von 1925 erhalten.1.8 g of isophorone diisocyanate and 6.7 g of the prepolymers described in Example 4 are dissolved in 60 g of 3-pentanone with exclusion of moisture. Then 6 g of coupler diol M-4 dissolved in 50 g of 3-pentanone are added at room temperature and the mixture is then stirred at boiling temperature for 3 h. Then 1.8 g of a 49.3% strength aqueous solution of the sodium salt of β'-aminoethyl-β-aminoethanesulfonic acid are added to the reaction solution and, after 15 minutes, 30 g of water are added dropwise within 3 minutes. After distilling off the solvent on the reaction evaporator and dialysis, a finely divided polyurethane yellow coupler latex with an equivalent molecular weight of 1925 is obtained.

Beispiel 7Example 7 Polyurethan-Purpurkuppler GPolyurethane purple coupler G

Zu einer Mischung aus 126 g (0,074 mol) Hexandiolneopentylglykol-polyadipat, 93 g der Verbindung M-12 und 400 ml trockenem Dioxan tropft man bei 100°C zügig eine Mischung aus 35,1 g Hexamethylendiisocyanat und 46,4 g lsophorondiisocanat. Nach 2-stündigem Erwärmen auf 100-1080C beträgt der NCO-Wert 2,9% (berechnet: 3,0%). Das Dioxan wird im Vakuum abdestilliert und durch 740 ml Aceton ersetzt. Nun versetzt man bei ca. 45°C mit einer Mischung aus 21 g einer 51,6 %igen wäßrigen Lösung des Natriumsalzes der β'-Aminoethyl-β-aminoethansulfosäure und 50 g Wasser. Man dispergiert nach 10 min mit 830 ml entsalztem Wasser. Man befreit im Vakuum vom Aceton und erhält eine feinteilige, lagerstabile Dispersion mit folgenden Daten:

Figure imgb0064
A mixture of 35.1 g of hexamethylene diisocyanate and 46.4 g of isophorone diisocanate is rapidly added dropwise at 100 ° C. to a mixture of 126 g (0.074 mol) of hexanediol neopentyl glycol polyadipate, 93 g of the compound M-12 and 400 ml of dry dioxane. After 2 hours of heating at 100-108 0 C the NCO value is 2.9% (calculated: 3.0%). The dioxane is distilled off in vacuo and replaced by 740 ml of acetone. A mixture of 21 g of a 51.6% strength aqueous solution of the sodium salt of β'-aminoethyl-β-aminoethanesulfonic acid and 50 g of water is then added at about 45 ° C. After 10 min, the mixture is dispersed with 830 ml of deionized water. The acetone is removed in vacuo and a finely divided, storage-stable dispersion is obtained with the following data:
Figure imgb0064

Die Einarbeitung der wäßrigen Dispersionen der erfindungsgemäßen Polyadditions- bzw. Polykondensationsprodukte in die Schichten von fotografischen Aufzeichnungsmaterialien erfolgt nach üblichen, dem Fachmann geläufigen Methoden. Hierzu wird ein wie zuvor beschrieben hergestellter Latex einer Gießlösung für eine lichtempfindliche oder nicht lichtempfindliche Schicht zugefügt und mit ihr innig vermischt, worauf die Mischung zur Schicht vergossen wird. Die Gießlösung enthält im allgemeinen ein hydrophiles Kolloid als Bindemittel, vorzugsweise Gelatine. Die erfindungsgemäßen Polyadditions- bzw. Polykondensationsprodukts können jedoch aufgrund ihrer hohen Dispersionsstabilität auch zu bindemittelarmen oder weitgehend bindemittelfreien Schichten vergossen werden.The aqueous dispersions of the polyaddition or polycondensation products according to the invention are incorporated into the layers of photographic recording materials by customary methods known to those skilled in the art. For this purpose, a latex prepared as described above is added to a casting solution for a light-sensitive or non-light-sensitive layer and mixed intimately with it, whereupon the mixture is poured into the layer. The casting solution generally contains a hydrophilic colloid as a binder, preferably gelatin. However, due to their high dispersion stability, the polyaddition or polycondensation product according to the invention can also be cast to form low-binder or largely binder-free layers.

Beispiel 8Example 8

Die Polyurethan-Purpurkupplerlatex D und E (Beispiel 4 und 5) und der Vergleichskuppler A wurden verschiedenen Proben einer Silberhalogenidemulsion zugemischt, die dem eingebrachten Farbkuppler entsprechend für Blau oder Grün sensibilisiert war. Die verwendete Silberhalogenidgelatine-Emulsion bestand aus 75 g Silberbromidjodid (lodidgehalt 3 mol-%) und 72 g Gelatine bezogen auf 1 kg Emulsion.The polyurethane magenta coupler latex D and E (example 4 and 5) and the comparative coupler A were mixed into different samples of a silver halide emulsion which was sensitized to blue or green according to the color coupler introduced. The silver halide gelatin emulsion used consisted of 75 g of silver bromide iodide (iodide content 3 mol%) and 72 g of gelatin based on 1 kg of emulsion.

Die so präparierten Emulsionen wurden auf mit einer Haftschicht versehene Cellulosetriacetatschichtträger aufgetragen und getrocknet.The emulsions prepared in this way were applied to cellulose triacetate layer supports provided with an adhesive layer and dried.

Fotografische Prüfung:

  • Die einzelnen Proben wurden mittels eines Sensitometers belichtet und danach in der unten beschriebenen Weise verarbeitet.
Photographic examination:
  • The individual samples were exposed using a sensitometer and then processed in the manner described below.

Bestimmt wurden relative Empfindlichkeit, Gradation (y), Farbausbeute und Stabilität des Farbbildes bei Lagerung der verarbeiteten Aufzeichnungsmaterialien unter verschiedenen Bedingungen (Farbdichteabnahme).

  • Lager 1: 7 Tage, 77°C, 5% relative Feuchte
  • Lager 2: 7 Tage, 60°C, gesättigte Feuchte
    • a: bei Maximaldichte gemessen
    • b: bei Dichte 0,5 gemessen
Relative sensitivity, gradation (y), color yield and stability of the color image were determined when the processed recording materials are stored under different conditions (decrease in color density).
  • Storage 1: 7 days, 77 ° C, 5% relative humidity
  • Storage 2: 7 days, 60 ° C, saturated humidity
    • a: measured at maximum density
    • b: measured at density 0.5

Verarbeitungsbäder:

  • Farbentwickler A
    Figure imgb0065
  • Bleichbad
    Figure imgb0066
  • Fixierbad Konzentrat (wird 1:3 mit Wasser verdünnt verwendet)
    Figure imgb0067
  • Stopp-Bad
    Figure imgb0068
  • Farbentwickler B
    Figure imgb0069
  • Verarbeitung
    Figure imgb0070
    Figure imgb0071
    Figure imgb0072
    Figure imgb0073
Processing baths:
  • Color developer A
    Figure imgb0065
  • Bleach bath
    Figure imgb0066
  • Fixing bath concentrate (used 1: 3 diluted with water)
    Figure imgb0067
  • Stop bath
    Figure imgb0068
  • Color developer B
    Figure imgb0069
  • processing
    Figure imgb0070
    Figure imgb0071
    Figure imgb0072
    Figure imgb0073

Aus den Werten der Tabelle 1 geht hervor, daß die erfindungsgemäßen Polyurethan-Purpurkupplerlatices in etwa mit dem Kuppler des Standes der Technik vergleichbar semitometrische Daten liefern, aber hinsichtlich des Feucht- und Trockenlagerverhaltens deutlich verbessert sind.It can be seen from the values in Table 1 that the polyurethane magenta coupler latices according to the invention provide semitometric data comparable to the coupler of the prior art, but are significantly improved with regard to the wet and dry storage behavior.

Beispiel 9Example 9

In einem weiteren Versuch wurden der Polyurethan-Gelbkupplerlatex F und der Vergleichskuppler B in Form einer Dibutylphthalat Emulsion in wäßriger Gelatine mit einem Dibutylphthalat/Vergleichskuppler B-Verhältnis von 1:1 wie in Beispiel 1 beschrieben auf eine Unterlage vergossen, belichtet und verarbeitet. Signifikante Unterschiede hinsichtlich der sensitometrischen Daten waren nicht meßbar. Die Proben wurden außerdem mit und ohne UV-Schutzfolie (UV-Schutzfolie mit einem 2-Hydroxyphenylbenztriazolderivat als absorbierender Substanz) dem Licht einer für Tageslicht normierten Xenonlampe ausgesetzt und mit 2,4.106 Lux-h belichtet. Die in Tabelle 2 angegebenen prozentualen Farbdichteabnahmen AD/Do wurden gemessen.

Figure imgb0074
In a further experiment, the polyurethane yellow coupler latex F and the comparative coupler B in the form of a dibutyl phthalate emulsion in aqueous gelatin were cast with a dibutyl phthalate / comparative coupler B ratio of 1: 1 as described in Example 1, exposed and processed. There were no significant differences in the sensitometric data. The samples were also exposed to and without UV protective film (UV protective film with a 2-hydroxyphenylbenztriazole derivative as the absorbing substance) to the light of a xenon lamp standardized for daylight and exposed to 2.4.10 6 lux-h. The percentage decrease in color density AD / Do given in Table 2 was measured.
Figure imgb0074

Aus Tabelle 2 geht hervor, daß der erfindungsgemäße Polyurethan-Gelbkupplerlatex gegenüber dem Vergleichskuppler eine erhöhte Stabilität gegenüber schädlicher Bestrahlung aufweist.Table 2 shows that the polyurethane yellow coupler latex according to the invention has an increased stability against harmful radiation compared to the comparative coupler.

Beispiel 10Example 10

Das Beispiel zeigt den Einfluß des erfindungsgemäßen Polyurethan-Gelbkupplerlatex F auf das Bruchverhalten von fotografischen Aufzeichnungsmaterialien.The example shows the influence of the polyurethane yellow coupler latex F according to the invention on the breaking behavior of photographic recording materials.

Auf einen präparierten Cellulosetriacetat-Filmträger wurde eine fotografische Emulsionsschicht, bestehend aus einer Silberbromidemulsion, einer erfindungsgemäß hergestellten Dispersion bzw. dem Vergleichsemulgat aus Beispiel 2, Gelatine une einem Härtungsmittel, hergestellt und getrocknet. Nach der Trocknung enthielt die Schicht des Vergleichsmaterials 30 Vol-% AgBr, 15 Vol-% Vergleichskuppler B, 15 Vol-% Dibutylphthalat und 40 Vol-% Gelatine. Bei dem erfindungsgemäßen Aufzeichnungsmaterial wurde anstelle von Vergleichskuppler B und Dibutylphthalat eine hinsichtlich der Kupplereinheiten äquivalente Menge an Polyurethan-Gelbkupplerlatex F eingesetzt. 36 mm breite Streifen dieser Aufzeichnungsmaterialien wurden 3 d in einem Klima von 20% r.F. bei 17°C angeglichen. Die Messung erfolgte nach der Schleifenmethode. Die Prüflinge werden dabei zu einer Schleife zusammengefügt und durch 3 Walzen, die in Form eines Dreiecks angeordnet sind, in Rotation gebracht. Dann wird die Zahl der Umdrehungen bestimmt, die zu einem Bruch des Filmmaterials führt und mit einem Material vergleichen, das wie oben beschrieben hergestellt wird und 30 Vol-% AgBr und 70 Vol-% Gelatine an Schichtbestandteilen enthält. Die Messungen brachten folgendes Ergebnis:A photographic emulsion layer consisting of a silver bromide emulsion, a dispersion prepared according to the invention or the comparative emulsifier from Example 2, gelatin and a hardening agent was prepared and dried on a prepared cellulose triacetate film support. After drying, the layer of the comparison material contained 30% by volume AgBr, 15% by volume Comparative Coupler B, 15% by volume dibutyl phthalate and 40% by volume gelatin. In the recording material according to the invention, instead of comparative coupler B and dibutyl phthalate, an amount of polyurethane yellow coupler latex F which was equivalent in terms of the coupler units was used. 36 mm wide strips of these recording materials were 3 d in a climate of 20% RH. adjusted at 17 ° C. The measurement was made using the loop method. The test specimens are put together in a loop and rotated by 3 rollers, which are arranged in the shape of a triangle. The number of revolutions which causes the film material to break is then determined and compared with a material which is produced as described above and contains 30% by volume AgBr and 70% by volume gelatin in layer components. The measurements gave the following result:

Figure imgb0075
Figure imgb0075

Der Versuch zeigt, daß durch die Verwendung der erfindungsgemäßen Polyurethanlatexkuppler das Bruchverhalten von fotografischen Aufzeichnungsmaterialien im Vergleich zu denjenigen mit emulgierten Farbkupplern verbessert wird.The experiment shows that the use of the polyurethane latex couplers according to the invention improves the fracture behavior of photographic recording materials compared to those with emulsified color couplers.

Claims (10)

1. Polyurea and polyurethane compounds optionally containing polyester and/or polyether structures and bearing recurring structural units corresponding to formula I:
Figure imgb0104
in which
Q is the n-bond residue of a photographically useful compound,
Y is -0- or ―NR1―,
R1 is H, C1-6 alkyl, cycloalkyl or phenyl,
n is an integer of 2 to 4.
2. Polyurea and polyurethane compounds as claimed in claim 1, characterized by a content of recurring structural units corresponding to the formula:
Figure imgb0105
in which
Q is the n-bond residue of a photographically useful compound;
Y is -0- or ―NR1―;
Z is the (p + 1)-bond residue of a (p + 1)-functional organic isocyanate compound;
R1 is H, C1-6 alkyl, cycloalkyl or phenyl;
n is an integer of 2 to 4;
p is an integer of ≥1.
3. Polyurea and polyurethane compounds as claimed in claim 1, characterized by a content of recurring structural units corresponding to formula II:
Figure imgb0106
in which
Q' either on its own or together with X (including ―L1―A3―L2―), represents the residue of a photographically useful compound,
X represents
Figure imgb0107
A1, A2 represent C1-4 alkylene,
A3 represents C1-8 alkylene, arylene or a chemical bond,
L' represents -CONH-, -NHCO-, -CO-, ―SO2―, ―O― or a chemical bond,
L2 represents -CONH-, -NH-, -0- or a chemical bond,
R' represents H, C1-6 alkyl, cycloalkyl or phenyl,
R2 represents H or C1-4 alkyl.
4. Polyurea and polyurethane compounds as claimed in claim 2, characterized by a content of recurring structural units corresponding to the formula
Figure imgb0108
in which
Q' either on its own or together with X (including ―L1―A3―L2―), represents the residue of a photographically useful compound,
X represents
Figure imgb0109
Y represents -0- or
Figure imgb0110
Z' is the two-bond residue of an organic diisocyanate compound,
A1, A2 represent C1-4 alkylene,
A3 represents C1-8 alkylene, arylene or a chemical bond,
L1 represents -CONH-, -NHCO-, -CO-, ―SO2―, -0- or a chemical bond,
L2 represents -CONH-, -NH-, -0- or a chemical bond,
R' represents H, C1-6 alkyl, cycloalkyl or phenyl,
R2 represents H or C1-4 alkyl.
5. Polyurea and polyurethane compounds as claimed in claim 1, characterized in that Q in formula I is part of a molecule which is capable of reacting with developer oxidation products.
6. An aqueous dispersion of the polyurea or polyurethane compound claimed in claim 1.
7. A photographic recording material comprising at least one photosensitive silver halide emulsion layer, characterized by a content of a polyurea or polyurethane compound optionally containing polyester and/or polyether structures and bearing recurring structural elements corresponding to formula I
Figure imgb0111
in which
Q is the n-bond residue of a photographically useful compound,
Y is -0- or ―NR1―,
R1 is H, C1-6 alkyl, cycloalkyl or phenyl,
n is an integer of 2 to 4.
8. A recording material as claimed in claim 7, characterized in that the polyurea or polyurethane compound contains recurring structural units corresponding to formula II
Figure imgb0112
in which
Q' either on its own or together with X (including ―L1―A3―L2―), represents the residue of a photographically useful compound,
X represents
Figure imgb0113
A1, A2 represent C1-4 alkylene,
A3 represents C1-8 alkylene, arylene or a chemical bond,
L1 represents -CONH-, -NHCO-, -CO-, ―SO2―, ―O― or a chemical bond,
L2 represents -CONH-, -NH-, -0- or a chemical bond,
R1 represents H, C1-6 alkyl, cycloalkyl or phenyl,
R2 represents H or C1-4 alkyl.
9. A photographic recording material as claimed in claim 7 or claim 8, characterized in that Q in formula I or Q' in formula II represents part of a molecule which is capable of reacting with developer oxidation products.
10. A photographic recording material as claimed in claim 9, characterized in that Q in formula I or Q' in formula II is the residue of a yellow, magenta, cyan or white coupler.
EP85115380A 1984-12-15 1985-12-04 Polyaddition or polycondensation products, their aqueous dispersions as well as a photographic recording material containing a photographic compound in the form of such polymeric products Expired - Lifetime EP0185248B1 (en)

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DE3708307A1 (en) * 1987-03-14 1988-09-22 Agfa Gevaert Ag COLOR PHOTOGRAPHIC RECORDING MATERIAL FOR THE COLOR DIFFUSION TRANSFER METHOD
DE68924627T2 (en) * 1988-09-01 1996-05-15 Eastman Kodak Co Color photographic element with polymeric couplers.
US5212015A (en) * 1989-06-14 1993-05-18 Minnesota Mining And Manufacturing Company Coated substrates comprising polymers derived from monocarbamate diols
US5093456A (en) * 1989-06-14 1992-03-03 Minnesota Mining And Manufacturing Company Monocarbamate diols, polymers derived from them and nlo-active materials therefrom
US5163060A (en) * 1989-06-14 1992-11-10 Minnesota Mining And Manufacturing Company Second harmonic generator comprising an NLO-active polymer derived from monocarbamate diols
CN105093804A (en) * 2014-12-16 2015-11-25 铜陵翔宇商贸有限公司 Stop bath used for photographic film and preparation method thereof

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US2671021A (en) * 1950-12-27 1954-03-02 Gen Aniline & Film Corp Polymeric magenta color former
BE648710A (en) * 1964-06-02 1964-10-01
DE1547860A1 (en) * 1965-12-30 1970-01-08 Fuji Photo Film Co Ltd Color photographic, photosensitive material
DE2041323A1 (en) * 1970-08-20 1972-02-24 Agfa Gevaert Ag Gelatin photographic layers with improved physical properties
DE2631521A1 (en) * 1976-07-14 1978-01-19 Agfa Gevaert Ag LIGHT-SENSITIVE PHOTOGRAPHIC MATERIAL WITH A LAYERING AGENT
DE3060639D1 (en) * 1979-02-16 1982-08-26 Eastman Kodak Co Coating composition containing a polyaniline salt semiconductor, a method of preparing said composition and an element with a conductive layer formed from said composition
US4237194A (en) * 1979-02-16 1980-12-02 Eastman Kodak Company Conductive polyanaline salt-latex compositions, elements and processes
DE3036846A1 (en) * 1980-09-30 1982-05-27 Agfa-Gevaert Ag, 5090 Leverkusen METHOD FOR PRODUCING DISPERSIONS OF HYDROPHOBIC SUBSTANCES IN WATER

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EP0185248A2 (en) 1986-06-25
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US4762777A (en) 1988-08-09

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